JP7639276B2 - Coloring composition for color filters and color filters - Google Patents

Description

The present invention relates to a coloring composition and a photosensitive coloring composition used in the manufacture of color filters used in color liquid crystal displays, color solid-state imaging devices, organic EL displays, quantum dot displays, electronic paper, and the like, as well as a color filter and a color liquid crystal display having filter segments formed using the same.

A color filter is formed by arranging two or more fine band-shaped filter segments of different hues in parallel (stripes) or crossing each other on a transparent substrate such as a glass substrate, or by arranging two or more fine filter segments of different hues in order in both the vertical and horizontal directions. The filter segments have small dimensions of several microns to several hundreds of microns, and are regularly arranged in a predetermined array for each hue.

On the color filters used in color liquid crystal display devices, transparent electrodes for driving the liquid crystal are generally formed by deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is further formed on top of the electrodes. In order to obtain sufficient performance from these transparent electrodes and alignment films, the formation process must be carried out at a high temperature, generally above 200°C, and preferably above 230°C.

In recent years, improved color reproducibility for displays has become an important trend. Specifically, filter segments are required to not discolor or lose film remaining rate even at high temperatures of 230°C or higher, but these properties tend to deteriorate in photosensitive coloring compositions that achieve high color reproducibility.

In order to solve these problems, various methods have been studied. For example, in Patent Document 1, discoloration during the drying process is prevented by using a colorant with high heat resistance. In Patent Document 2, discoloration during the drying process is prevented by improving the heat resistance of a resin-type dispersant. In Patent Document 3, a high-sensitivity polymerization initiator is used to prevent a decrease in the remaining film rate during the drying process. However, the high heat resistance and remaining film rate required for color filters today have not been fully achieved, and further improvements are required. It is even more difficult to achieve both heat resistance and remaining film rate at the moment. Furthermore, in recent years, the pixels of liquid crystal display devices have become finer, and a very high level of filterability is required in filter filtration for removing foreign matter from colored compositions and photosensitive colored compositions. In Patent Document 4, high heat resistance and remaining film rate are achieved by using a crosslinked dispersant, but there is no description regarding filterability.

JP 2020-33458 A JP 2019-218547 A JP 2017-097319 A JP 2009-155406 A

The present invention aims to provide a coloring composition having excellent heat resistance, film remaining rate, storage stability, and filterability, a photosensitive coloring composition having excellent heat resistance, film remaining rate, adhesion, storage stability, and filterability, and a color filter and a color liquid crystal display device formed using the coloring composition.

As a result of intensive research to solve the above problems, the present inventors have found that a coloring composition containing two types of acidic resin-type dispersants having a vinyl polymer portion has excellent heat resistance, film remaining rate, adhesion, storage stability, and filterability, and have made the present invention based on this finding.
That is, the present invention relates to a coloring composition comprising a colorant (A) and an acidic resin-type dispersant (C) having a vinyl polymer portion, the acidic resin-type dispersant (C) comprising the following acidic resin-type dispersant (C1) and acidic resin-type dispersant (C2).
Acidic resin-type dispersant (C1): A resin-type dispersant in which the content of structural units derived from an ethylenically unsaturated monomer having an oxetane group is 20% by mass or more and 100% by mass or less, when the vinyl polymerization portion of the resin-type dispersant is taken as 100% by mass.
Acidic resin-type dispersant (C2): A resin-type dispersant that does not contain a structural unit derived from an ethylenically unsaturated monomer having an oxetane group.

The present invention also relates to the coloring composition, characterized in that the acidic resin-type dispersant (C1) and/or (C2) has a polyester portion having a carboxyl group, which is formed by reacting an acid anhydride group in one or more acid anhydrides selected from tetracarboxylic acid anhydrides and tricarboxylic acid anhydrides with a hydroxyl group in a hydroxyl group-containing compound, and a vinyl polymer portion formed by radical polymerization of an ethylenically unsaturated monomer.

The present invention also relates to the above coloring composition, characterized in that the colorant (A) contains a copper phthalocyanine pigment.

The present invention also relates to the coloring composition, characterized in that the content of the acidic resin-type dispersant (C1) is 30% by mass or more and less than 70% by mass, based on 100% by mass of the total of the acidic resin-type dispersant (C1) and the acidic resin-type dispersant (C2).

The present invention also relates to the coloring composition, further comprising a dye derivative (B).

The present invention also relates to the coloring composition, further comprising a polymerizable compound (D) and/or a photopolymerization initiator (E).

The present invention also relates to a color filter having filter segments formed using the coloring composition.

The present invention also relates to a liquid crystal display device equipped with the above-mentioned color filter.

The present invention provides a coloring composition having excellent heat resistance, film remaining rate, storage stability, and filterability, a photosensitive coloring composition having excellent heat resistance, film remaining rate, adhesion, storage stability, and filterability, and a color filter and a color liquid crystal display device formed using the photosensitive coloring composition.

The constituent features of the present invention will be described in detail below.
In this application, unless otherwise specified, the terms "(meth)acryloyl", "(meth)acrylic", "(meth)acrylic acid", or "(meth)acrylate" refer to "acryloyl and/or methacryloyl", "acrylic and/or methacrylic", "acrylic acid and/or methacrylic acid", or "acrylate and/or methacrylate", respectively. In addition, "C.I." in this specification means Color Index (C.I.).

The colored composition of the present invention contains a colorant (A) and an acidic resin-type dispersant (C) having a vinyl polymer portion, and is characterized in that the acidic resin-type dispersant (C) contains the following acidic resin-type dispersant (C1) and acidic resin-type dispersant (C2).
Acidic resin type dispersant (C1): An acidic resin type dispersant in which the content of a structural unit derived from an ethylenically unsaturated monomer having an oxetane group is 20% by mass or more and 100% by mass or less, when the vinyl polymerization portion of the acidic resin type dispersant is taken as 100% by mass.
Acidic resin type dispersant (C2): An acidic resin type dispersant that does not contain a structural unit derived from an ethylenically unsaturated monomer having an oxetane group.

<Colorant (A)>
The colorant (A) in the present invention may contain a pigment, a dye, or other colorant. As the pigment, an organic or inorganic pigment may be used alone or in combination of two or more kinds. As the pigment, a pigment having high color development and high heat resistance, particularly a pigment having high thermal decomposition resistance, is preferred, and an organic pigment is usually used. Specific examples of organic pigments that can be used in the coloring composition are shown below with their color index numbers.

The red coloring material may be, for example, C.I. Pigment Red 7, 9, 14, 41, 48:1, 48:2, 48:3, 48:4, 57:1, 81, 81:1, 81:2, 81:3, 81:4, 97, 122, 123, 146, 149, 150, 168, 169, 176, 177, 178, 180, 184, 185, 187, 192, 200, 202, 208, 209, 210, 215 , 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 246, 254, 255, 264, 268, 270, 272, 273, 274, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, or 287. As an orange colorant, an orange pigment such as C.I. Pigment Orange 36, 38, 43, 51, 55, 59, 61, 71, or 73 can be used. As a yellow colorant, C.I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65 , 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 12 Yellow pigments such as 6, 127, 128, 129, 137, 138, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, 221, or 231 can be used.

As the green coloring material, for example, green pigments such as C.I. Pigment Green 7, 10, 36, 37, 58, 62, and 63 can be used. It is also preferable to use aluminum phthalocyanine pigments, and aluminum phthalocyanine pigments such as those described in JP-A-2004-333817 and Japanese Patent No. 4893859 can also be used.

As the blue colorant, for example, blue pigments such as C.I. Pigment Blue 1, 1:2, 1:3, 2, 2:1, 2:2, 3, 8, 9, 10, 10:1, 11, 12, 15, 15:1, 15:2, 15:3, 15:4, 16, 18, 19, 22, 24, 24:1, 53, 56, 56:1, 57, 58, 59, 60, 61, 62, and 64 can be used. As the purple colorant, purple pigments such as C.I. Pigment Violet 1, 19, 27, 29, 30, 32, 37, 40, 42, and 50 can be used in combination. It is also preferable to use aluminum phthalocyanine pigments, such as those described in JP-A-2004-333817 and Japanese Patent No. 4893859.

Examples of inorganic pigments include titanium oxide, barium sulfate, zinc oxide, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron (III) oxide), cadmium red, ultramarine, Prussian blue, chromium oxide green, cobalt green, umber, synthetic iron black, etc. Inorganic pigments are used in combination with organic pigments to ensure good coatability, sensitivity, developability, etc. while maintaining a balance between saturation and brightness.

Other colorants can be used alone or in combination of two or more types.

From the viewpoint of heat resistance, the colorant (A) in the present invention is preferably a copper phthalocyanine pigment such as C.I. Pigment Blue 15:1, C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:6, or C.I. Pigment Blue 17, and among these, C.I. Pigment Blue 15:6 is more preferable.

The colorant (A) is preferably present in an amount of 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, based on the total solid content of the coloring composition. The upper limit is preferably 80% by mass or less, more preferably 75% by mass or less, and even more preferably 70% by mass or less.

Dyes can also be used in the present invention. Examples include anthraquinone dyes, monoazo dyes, disazo dyes, oxazine dyes, aminoketone dyes, xanthene dyes, quinoline dyes, and triphenylmethane dyes. When using dyes, it is effective to incorporate the dye into the resin using the polar group of anionic or cationic dyes to impart solubility in organic solvents.

Specific examples of usable anionic dyes are shown below with their color index numbers.

Red dyes include C.I. Acid Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 22, 23, 24, 25, 25:1, 26, 26:1, 26:2, 27, 29, 30, 31, 32, 33, 34, 35, 36, 37, 39, 40, 41, 42, 43, 44, 45, 47, 50, 52, 53, 54, 55, 5 6, 57, 59, 60, 62, 64, 65, 66, 67, 68, 70, 71, 73, 74, 76, 76:1, 80, 81, 82, 83, 85, 86, 87, 88, 89, 91, 92, 93, 97, 99, 102, 104, 106, 107, 108, 110, 111, 113, 114, 115, 116, 120, 123, 125, 127, 128, 131 , 132, 133, 134, 135, 137, 138, 141, 142, 143, 144, 148, 150, 151, 152, 154, 155, 157, 158, 160, 16 1, 163, 164, 167, 170, 171, 172, 173, 175, 176, 177, 181, 229, 231, 237, 239, 240, 241, 242, 249, 2 52, 253, 255, 257, 260, 263, 264, 266, 267, 274, 276, 280, 286, 289, 299, 306, 309, 311, 323, 333, 324, 325, 326, 334, 335, 336, 337, 340, 343, 344, 347, 348, 350, 351, 353, 354, 356, 388, etc.

Also, C.I. Direct Red 1, 2, 2:1, 4, 5, 6, 7, 8, 10, 10:1, 13, 14, 15, 16, 17, 18, 21, 22, 23, 24, 26, 26:1, 28, 29, 31, 33, 33:1, 34, 35, 36, 37, 39, 42, 43, 43:1, 44, 46, 49, 5 2, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 67, 67:1, 68, 72, 72:1, 73, 74, 75, 77, 78, 79, 81, 81:1, 85, 86, 88, 89, 90, 97, 100, 101, 101:1, 107, 108, 110, 114, 1 16, 117, 120, 121, 122, 122:1, 124, 125, 127, 127:1, 127:2, 128, 129, 130, 13 2, 134, 135, 136, 137, 138, 140, 141, 148, 149, 150, 152, 153, 154, 155, 156, 1 69, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 186, 189, 204, 211, 213, 214, 217, 222, 224, 225, 226, 227, 228, 232, 236, 237, 238, etc. can also be used.

Yellow dyes include C.I. Acid Yellow 2, 3, 4, 5, 6, 7, 8, 9, 9:1, 10, 11, 11:1, 12, 13, 14, 15, 16, 17, 17:1, 18, 20, 21, 22, 23, 25, 26, 27, 29, 30, 31, 33, 34, 36, 38, 39, 40, 40:1, 41, 42, 42:1, 43, 44, 46, 48, 51, 53, 55, 56, 60, 63, 65, 66, 67, 68 , 69, 72, 76, 82, 83, 84, 86, 87, 90, 94, 105, 115, 117, 122, 127, 131, 132, 136, 141, 142, 143, 144, 145, 146, 149, 153, 159, 166, 168, 169, 172, 174, 175, 178, 180, 183, 187, 188, 189, 190, 191, 192, 199, etc.

C.I. Direct Yellow 1, 2, 4, 5, 12, 13, 15, 20, 24, 25, 26, 32, 33, 34, 35, 41, 42, 44, 44:1, 45, 46, 48, 49, 50, 51, 61, 66, 67, 69, 70, 71, 72, 73, 74, 81, 84, 86, 90, 91, 92, 95, 107, 110, 117, 118, 119, 120, 121, 126, 127, 129, 132, 133, 134, etc. can also be used.

Examples of orange dyes include C.I. Acid Orange 1, 1:1, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 17, 18, 19, 20, 20:1, 22, 23, 24, 24:1, 25, 27, 28, 28:1, 30, 31, 33, 35, 36, 37, 38, 41, 45, 49, 50, 51, 54, 55, 56, 59, 79, 83, 94, 95, 102, 106, 116, 117, 119, 128, 131, 132, 134, 136, and 138.
Also usable are C.I. Direct Orange 1, 2, 3, 4, 5, 6, 7, 8, 10, 13, 17, 19, 20, 21, 24, 25, 26, 29, 29:1, 30, 31, 32, 33, 43, 49, 51, 56, 59, 69, 72, 73, 74, 75, 76, 79, 80, 83, 84, 85, 87, 88, 90, 91, 92, 95, 96, 97, 98, 101, 102, 102:1, 104, 108, 112, 114, etc.

Blue dyes include C.I. Acid Blue 1, 2, 3, 4, 5, 6, 7, 8, 9, 11, 13, 14, 15, 17, 19, 21, 22, 23, 24, 25, 26, 27, 29, 34, 35, 37, 40, 41, 41:1, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 5 5, 56, 57, 58, 62, 62:1, 63, 64, 65, 68, 69, 70, 73, 75, 78, 79, 80, 81, 83, 8485 , 86, 88, 89, 90, 90:1, 91, 92, 93, 95, 96, 99, 100, 103, 104, 108, 109, 110, 111 , 112, 113, 114, 116, 117, 118, 119, 120, 123, 124, 127, 127:1, 128, 129, 135 , 137, 138, 143, 145, 147, 150, 155, 159, 169, 174, 175, 176, 183, 198, 203, 20 4, 205, 206, 208, 213, 227, 230, 231, 232, 233, 235, 239, 245, 247, 253, 257, 258, 260, 261, 262, 264, 266, 269, 271, 272, 273, 274, 277, 278, 280, etc.

Also, C.I. Direct Blue 1, 2, 3, 4, 6, 7, 8, 8:1, 9, 10, 12, 14, 15, 16, 19, 20, 21, 21:1, 22, 23, 25, 27, 29, 31, 35, 36, 37, 40, 42, 45, 48, 49, 50, 53, 54, 55, 58, 60, 61, 64, 65, 67, 79, 96, 97, 98:1, 101, 106, 107, 108, 109, 111, 116, 122, 123, 124, 128, 129, 130, 13 0:1, 132, 136, 138, 140, 145, 146, 149, 152, 153, 154, 156, 158, 158:1, 164, 165, 166, 167, 168, 169, 170, 174, 177, 181, 184, 185, 188, 190, 192, 193, 206, 207, 209, 213, 215, 225, 226, 229, 230, 231, 242, 243, 244, 253, 254, 260, 263, etc. can also be used.

Purple dyes include C.I. Acid Violet 1, 2, 3, 4, 5, 5:1, 6, 7, 7:1, 9, 11, 12, 13, 14, 15, 16, 17, 19, 20, 21, 23, 24, 25, 27, 29, 30, 31, 33, 34, 36, 38, 39, 41, 42, 43, 47, 49, 51, 63, 67, 72, 76, 96, 97, 102, 103, 109, etc.

Also, C.I. Direct Violet 1, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 16, 17, 18, 21, 22, 25, 26, 27, 28, 29, 30, 31, 32, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 45, 51, 52, 54, 57, 58, 61, 62, 63, 64, 71, 72, 77, 78, 79, 80, 81, 82, 83, 85, 86, 87, 88, 93, 97, etc. can be used.

Examples of green dyes include C.I. Acid Green 2, 3, 5, 6, 7, 8, 9, 10, 11, 13, 14, 15, 16, 17, 18, 19, 20, 22, 25, 25:1, 27, 34, 36, 37, 38, 40, 41, 42, 44, 54, 55, 59, 66, 69, 70, 71, 81, 84, 94, and 95.
Also usable are C.I. Direct Green 11, 13, 14, 24, 30, 34, 38, 42, 49, 55, 56, 57, 60, 78, 79, 80, and the like.

Specific examples of cationic dyes that can be used are shown below with their color index numbers.

Triphenylmethane cationic dyes include C.I. Basic Violet 1 (Methyl Violet), 3 (Crystal Violet), 14 (Magenta), C.I. Basic Blue 1 (Basic Cyanine 6G), 5 (Basic Cyanine EX), 26 (Victoria Blue B conc.), C.I. Basic Green 1 (Brilliant Green GX), and 4 (Malachite Green).

Examples of xanthene cationic dyes include C.I. Basic Red 1 (Rhodamine 6G, 6GCP), 3, and 8 (Rhodamine G). Of these, it is preferable to use C.I. Basic Red 1.

Examples of cyanine cationic dyes include C.I. Basic Yellow 11, 21, and 28.

Anthraquinone cationic dyes include C.I. Basic Blue 72, flavin cationic dyes include C.I. Basic Yellow 1, auramine cationic dyes include C.I. Basic Yellow 2 and 3, safranine cationic dyes include C.I. Basic Red 2, acridine cationic dyes include C.I. Basic Yellow 5, oxazine cationic dyes include C.I. Basic Blue 3, thiazine cationic dyes include C.I. Basic Blue 24, and methylene blue cationic dyes include C.I. Basic Blue 9 (Methylene Blue FZ, Methylene Blue B), 25 (Basic Blue GO), and 24 (New Methylene Blue NX). Among them, it is preferable to use C.I. Basic Yellow 1, 9, 24, and 25.

Another example of a squarylium-based cationic dye is (SQ-1K) described in JP 2017-114956 A.

<Minification of pigment>
When the colorant used in the coloring composition of the present invention is a pigment, it is preferable to use it after it has been finely divided from the viewpoint of transmittance. The method of finely dividing is not particularly limited, and examples thereof include wet grinding, dry grinding, and dissolution and deposition methods. Among these, salt milling treatment using a kneader method, which is a type of wet grinding, is preferable. The average primary particle size of the pigment as determined by TEM (transmission electron microscope) is preferably 5 to 90 nm, and more preferably 10 to 70 nm. If the pigment has an appropriate particle size, dispersibility is improved, and the contrast ratio is also improved.

Salt milling is a process in which a mixture of pigment, water-soluble inorganic salt, and water-soluble organic solvent is mechanically kneaded while heating using a batch or continuous mixer such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, sand mill, or planetary mixer, and then the water-soluble inorganic salt and water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt acts as a crushing aid, and the high hardness of the inorganic salt is used to crush the pigment during salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment with a very fine primary particle size, a narrow distribution range, and a sharp particle size distribution.

Examples of water-soluble inorganic salts include sodium chloride, potassium chloride, and sodium sulfate. Among these, sodium chloride (table salt) is preferable because it is inexpensive. From the viewpoints of both processing efficiency and production efficiency, it is preferable to use 50 to 2,000 parts by weight of the water-soluble inorganic salt per 100 parts by weight of the pigment, and more preferably 300 to 1,000 parts by weight.

The water-soluble organic solvent is not particularly limited as long as it functions to wet the pigment and the water-soluble inorganic salt, dissolves (is miscible with) water, and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent becomes prone to evaporate, a high-boiling solvent with a boiling point of 120°C or higher is preferred from the standpoint of safety. For example, 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, etc. may be used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by mass, more preferably 50 to 500 parts by mass, per 100 parts by mass of the pigment.

When the pigment is subjected to salt milling, a resin may be added as necessary. There are no particular limitations on the type of resin used, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, etc. may be used. The resin used is preferably solid at room temperature and insoluble in water, and more preferably partially soluble in the organic solvents mentioned above. The amount of resin used is preferably 5 to 200 parts by mass per 100 parts by mass of the pigment.

<Dye derivative (B)>
In the present invention, it is preferable to use a dye derivative from the viewpoint of agglomerated foreign matter. As the dye derivative (B) used in the present invention, a dye derivative having a functional group introduced into the dye matrix skeleton, which is an organic dye residue, can be used. These can be classified into acidic, basic, and neutral depending on the chemical structure of the functional group introduced into the dye matrix skeleton. For example, acidic dye derivatives include compounds having acidic substituents such as sulfo groups, carboxy groups, and phosphate groups, and amine salts thereof. Basic dye derivatives include compounds having basic substituents such as sulfonamide groups and tertiary amino groups at the terminals. Neutral dye derivatives include compounds having neutral substituents such as phenyl groups and phthalimidoalkyl groups.
Examples of the dye matrix skeleton which is an organic dye residue include diketopyrrolopyrrole pigments, phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazineindigo pigments, triazine pigments, benzimidazolone pigments, indole pigments such as benzoisoindole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, threne pigments, metal complex pigments, azo pigments such as azo, disazo, polyazo, etc. Among these, a phthalocyanine matrix skeleton is more preferable from the viewpoint of suppressing generation of foreign matter over time.
Specifically, diketopyrrolopyrrole dye derivatives are described in JP2001-220520A, WO2009/081930, WO2011/052617, WO2012/102399, and JP2017-156397A. Phthalocyanine dye derivatives are described in JP2007-226161A, W2016/163351A, JP2017-165820A, and Japanese Patent No. 5753266A. Anthraquinone dye derivatives are described in JP2007-226161A, WO2016/163351A, JP2017-165820A, and Japanese Patent No. 5753266A. JP-A-63-264674, JP-A-09-272812, JP-A-10-245501, JP-A-10-265697, JP-A-2007-079094, WO2009/025325 pamphlet; quinacridone dye derivatives are shown in JP-A-48-54128, JP-A-03-9961, and JP-A-2000-273383; dioxazine dye derivatives are shown in JP-A-2011-162662; thiazine indigo dye derivatives are shown in JP-A-2007-314785 As triazine-based dye derivatives, see JP-A-61-246261, JP-A-11-199796, JP-A-2003-165922, JP-A-2003-168208, JP-A-2004-217842, and JP-A-2007-314681; as benzoisoindole-based dye derivatives, see JP-A-2009-57478; as quinophthalone-based dye derivatives, see JP-A-2003-167112, JP-A-2006-291194, JP-A-2008-31281, and JP-A-2012-2 Examples of naphthol-based dye derivatives include those described in JP-A-2012-208329 and JP-A-2014-5439; examples of azo-based dye derivatives include those described in JP-A-2001-172520 and JP-A-2012-172092; examples of acidic substituents include those described in JP-A-2004-307854; and examples of basic substituents include those described in JP-A-2002-201377, JP-A-2003-171594, JP-A-2005-181383, and JP-A-2005-213404. In these documents, the dye derivative is sometimes described as a derivative, a pigment derivative, a dispersant, a pigment dispersant, or simply a compound, but the compound having a substituent such as an acidic group, a basic group, or a neutral group in the dye base skeleton, which is the above-mentioned organic dye residue, is synonymous with the dye derivative.
These dye derivatives can be used alone or in combination of two or more kinds.

The dye derivative (B) in the present invention is preferably a diketopyrrolopyrrole dye derivative, a dioxazine dye derivative, or a phthalocyanine dye derivative, and among these, a phthalocyanine derivative is particularly preferred.
<Acidic Resin-Type Dispersant (C)>

The acidic resin-type dispersant (C) in the present invention is characterized by containing the following acidic resin-type dispersant (C1) and acidic resin-type dispersant (C2).
Acidic resin type dispersant (C1): An acidic resin type dispersant in which the content of a structural unit derived from an ethylenically unsaturated monomer (c1) having an oxetane group is 20% by mass or more and 100% by mass or less, when the vinyl polymerization portion of the resin type dispersant is taken as 100% by mass.
Acidic resin type dispersant (C2): An acidic resin type dispersant that does not contain a structural unit derived from an ethylenically unsaturated monomer (c1) having an oxetane group.
This provides excellent effects in terms of high heat resistance, film remaining rate, adhesion, storage stability, and filterability. The resin-type dispersant may also contain other resin-type dispersants such as acidic resin-type dispersants other than those described above, and basic resin-type dispersants having an amine value.

Examples of acidic dispersants include those that have a carboxyl group, a sulfone group, a phosphate group, etc. in the resin, but from the viewpoint of viscosity stability and heat resistance, resin-type dispersants that have a carboxyl group are preferred. Resin-type dispersants that have a carboxyl group may be shaped as a straight-chain resin-type dispersant or a comb-type resin-type dispersant. In the present invention, a comb-type resin-type dispersant that has a carboxyl group is preferred.

<Straight-chain acidic resin-type dispersant>
All linear resin-type dispersants having a carboxyl group can be produced using known methods, and can be synthesized using known methods such as those shown in, for example, JP-A-2009-251481, JP-A-2007-23195, and JP-A-1996-143651. As an example of a method for producing a linear dispersant, a dispersant having a carboxyl group can be produced by adding a tricarboxylic anhydride to the hydroxyl group of a vinyl polymer having one hydroxyl group at one end as a raw material.

<Comb-shaped acidic resin-type dispersant>
As the comb-shaped acidic resin-type dispersant, the acidic resin-type dispersant (C1) and/or (C2) is preferably a comb-shaped resin-type dispersant obtained by radical polymerization of a polyester portion having a carboxyl group, which is obtained by reacting an acid anhydride group in one or more acid anhydrides (b) selected from tetracarboxylic anhydrides (b1) and tricarboxylic anhydrides (b2) with a hydroxyl group in a hydroxyl-group-containing compound (a), and an ethylenically unsaturated monomer (c). This makes it possible to efficiently prevent aggregation of the colorant and to exhibit excellent storage stability.
The dispersant of the present invention is composed of two moieties, and since it is impossible or almost unrealistic to specify and describe how these moieties are bonded, it will be described based on the production method.

Next, each of the components of the acidic resin-type dispersants (C1) and (C2) will be described.
[Hydroxyl-containing compound (a)]
The hydroxyl group-containing compound is not particularly limited as long as it has a hydroxyl group in the molecule, but is preferably a polyol having two or more hydroxyl groups in the molecule, and particularly preferably a compound (a1) having two hydroxyl groups and one thiol group in the molecule.

[Compound (a1) having two hydroxyl groups and one thiol group in the molecule]
Examples of the compound (a1) having two hydroxyl groups and one thiol group in the molecule include 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2-propanediol (thioglycerin), 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, and 2-mercaptoethyl-2-ethyl-1,3-propanediol.

[Other polyols (a2)]
Other usable polyols (a2) include, to name only representative ones, those belonging to the following groups (1) to (7). By using these polyol compounds in combination, it becomes easy to adjust the density of the carboxylic acid group and the proportion of the solvent-soluble portion.

(1) Polyhydric alcohols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,4-bis(hydroxymethyl)cyclohexane, bisphenol A, hydrogenated bisphenol A, hydroxypivalyl hydroxypivalate, trimethylolethane, trimethylolpropane, 2,2,4-trimethyl-1,3-pentanediol, glycerin, or hexanetriol;

(2) Various polyether glycols such as polyoxyethylene glycol, polyoxypropylene glycol, polyoxyethylene polyoxytetramethylene glycol, polyoxypropylene polyoxytetramethylene glycol, or polyoxyethylene polyoxypropylene polyoxytetramethylene glycol;

(3) Modified polyether polyols obtained by ring-opening polymerization of the above-mentioned various polyhydric alcohols with (cyclic) ether bond-containing compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, or allyl glycidyl ether;

(4) Polyester polyols obtained by co-condensation of one or more of the above-mentioned various polyhydric alcohols with polyvalent carboxylic acids, in which the polyvalent carboxylic acids are particularly represented by succinic acid, adipic acid, sebacic acid, azelaic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,5-hexanetricarboxylic acid, 1,4-cyclohexanetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexatricarboxylic acid, or 2,5,7-naphthalenetricarboxylic acid;

(5) Lactone-based polyester polyols obtained by polycondensation reaction of one or more of the above-mentioned various polyhydric alcohols with various lactones such as ε-caprolactone, δ-valerolactone, or 3-methyl-δ-valerolactone, or lactone-modified polyester polyols obtained by polycondensation reaction of the above-mentioned various polyhydric alcohols with polycarboxylic acids and various lactones;

(6) Epoxy-modified polyester polyols obtained by using one or more epoxy compounds, such as bisphenol A type epoxy compounds, hydrogenated bisphenol A type epoxy compounds, glycidyl ethers of monohydric and/or polyhydric alcohols, or glycidyl esters of monobasic and/or polybasic acids, in combination during the synthesis of polyester polyol; or

(7) Other polymer polyols such as polyester polyamide polyols, polycarbonate polyols, polybutadiene polyols, polypentadiene polyols, castor oil, castor oil derivatives, hydrogenated castor oil, hydrogenated castor oil derivatives, hydroxyl group-containing acrylic copolymers, hydroxyl group-containing fluorine-containing compounds, and hydroxyl group-containing silicone resins.

The optional other polyols (a2) shown in (1) to (7) may of course be used alone or in combination of two or more kinds, but from the viewpoint of compatibility and dispersion stability, the weight average molecular weight is preferably 40 to 10,000, more preferably 100 to 2,000, and even more preferably 100 to 1,000. If the weight average molecular weight is less than 40, the effect of improving compatibility and dispersion stability is small, and if the weight average molecular weight is 10,000 or more, compatibility may worsen.

The number of hydroxyl groups in one molecule of the other polyol (a2) is not particularly limited as long as the desired dispersant can be synthesized, but a diol is preferred. In particular, by reacting with the tetracarboxylic dianhydride (b1), carboxyl groups that serve as pigment adsorption groups can be arranged regularly in the main chain, which is advantageous for pigment dispersion. If a large amount of polyol with more than two hydroxyl groups is used, the main chain of the polyester will branch, becoming complex and bulky, and it may become difficult to achieve a dispersion effect. From a design perspective, such as adjusting the molecular weight of the polyester (X) and adjusting the viscosity of the dispersion, it should be kept to a minimum.

[Acid anhydride (b)]
The acid anhydride (b) of the present invention contains at least one selected from the group consisting of tetracarboxylic acid anhydrides (b1) and tricarboxylic acid anhydrides (b2).
The two anhydride groups of the tetracarboxylic dianhydride (b1) react with the hydroxyl groups of the hydroxyl group-containing compound (a), thereby enabling carboxyl groups, which serve as pigment-adsorbing groups, to be regularly arranged in the main chain of the dispersant (X), which is advantageous for pigment dispersion.
When a tricarboxylic anhydride (b2) is used, it reacts with a hydroxyl group to form an ester bond, leaving a carboxyl group.

In addition, polycarboxylic acid anhydrides other than tetracarboxylic acid anhydrides (b1) and tricarboxylic acid anhydrides (b2), such as dicarboxylic acid anhydrides and anhydrides of compounds having five or more carboxylic acids, can also be used in combination.

[Tetracarboxylic acid anhydride (b1)]
The tetracarboxylic dianhydride (b1) used in the present invention is,
1,2,3,4-butane tetracarboxylic dianhydride, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic dianhydride, 3,5,6-tricarboxynorbornane-2-acetic dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 5-(2,5-dioxotetrahydrofural)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo[2,2,2]-oct-7-ene-2,3,5,6-tetracarboxy aliphatic tetracarboxylic dianhydrides such as carboxylic dianhydride, pyromellitic dianhydride, ethylene glycol ditrimellitic anhydride, propylene glycol ditrimellitic anhydride, butylene glycol ditrimellitic anhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenylsulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylsilane tetracarboxylic acid dianhydride, 3,3',4,4'-tetraphenylsilane tetracarboxylic dianhydride, 1,2,3,4-furan tetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidenediphthalic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic dianhydride, bis(phthalic acid)phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic ) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid dianhydride, or aromatic tetracarboxylic acid dianhydride such as 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalene succinic acid dianhydride.

The tetracarboxylic dianhydride used in the present invention is not limited to the compounds exemplified above, and may have any structure as long as it has two carboxylic anhydride groups. These may be used alone or in combination. Tetracarboxylic dianhydride forms a dispersant having two carboxyl groups per polyester unit by reaction with polyol, and is therefore preferred as a component of the dispersant (X) of the present invention from the viewpoint of pigment adsorption.

Furthermore, from the viewpoint of adsorption to colorants, aromatic tetracarboxylic dianhydrides are preferably used in the present invention, and more preferably, tetracarboxylic dianhydrides having two or more aromatic rings. Aromatic carboxylic acids have a higher pigment adsorption ability than aliphatic carboxylic acids, and furthermore, carboxylic acids having two or more aromatic rings have a skeleton suitable for pigment adsorption and also have high heat resistance.

Specific examples include aromatic tetracarboxylic dianhydrides represented by the following general formula (1) or (2).

［一般式（１）中、ｋは１または２である。］ General formula (1):

[In general formula (1), k is 1 or 2.]

General formula (2):


[In general formula (2), Q1 is a direct bond, -O-, -CO-, -COOCH2CH2OCO-, -SO2-, -C(CF3)2-, general formula (3):

で表される基、または一般式（４）：

or a group represented by general formula (4):

で表される基である。］

It is a group represented by the following formula:

[Tricarboxylic acid anhydride (b2)]
Examples of the tricarboxylic acid anhydride (b2) include aliphatic tricarboxylic acid anhydrides and aromatic tricarboxylic acid anhydrides.

Examples of aliphatic tricarboxylic anhydrides include 3-carboxymethylglutaric anhydride, 1,2,4-butanetricarboxylic acid-1,2-anhydride, cis-propene-1,2,3-tricarboxylic acid-1,2-anhydride, and 1,3,4-cyclopentanetricarboxylic acid anhydride.

Examples of aromatic tricarboxylic acids include benzenetricarboxylic anhydrides (1,2,3-benzenetricarboxylic anhydride, trimellitic anhydride [1,2,4-benzenetricarboxylic anhydride], etc.), naphthalenetricarboxylic anhydrides (1,2,4-naphthalenetricarboxylic anhydride, 1,4,5-naphthalenetricarboxylic anhydride, 2,3,6-naphthalenetricarboxylic anhydride, 1,2,8-naphthalenetricarboxylic anhydride, etc.), 3,4,4'-benzophenonetricarboxylic anhydride, 3,4,4'-biphenylethertricarboxylic anhydride, 3,4,4'-biphenyltricarboxylic anhydride, 2,3,2'-biphenyltricarboxylic anhydride, 3,4,4'-biphenylmethanetricarboxylic anhydride, and 3,4,4'-biphenylsulfonetricarboxylic anhydride. Among the above, aromatic tricarboxylic anhydrides are preferably used in the present invention from the viewpoint of adsorption to pigments.

The ratio of the acid anhydride group in the one or more acid anhydrides (b) selected from the tetracarboxylic acid anhydrides (b1) and the tricarboxylic acid anhydrides (b2) to the hydroxyl group in the hydroxyl group-containing compound (a) is
The ratio of acid anhydride groups to hydroxyl groups is preferably 0.5 to 1.5.
If the ratio is less than 0.5 or more than 1.5, a large portion will not react, and the desired dispersant will not be obtained in many cases.

[Ethylenically unsaturated monomer (c)]
The dispersant (C) of the present invention is characterized in that it contains an acidic resin-type dispersant (C1) having a vinyl polymer portion obtained by radical polymerization of an ethylenically unsaturated monomer (c), and in which the content of structural units derived from an ethylenically unsaturated monomer having an oxetane group is 20% by mass or more and 100% by mass or less, when the vinyl polymerization portion of the resin-type dispersant is taken as 100% by mass, and an acidic resin-type dispersant (C2) that does not contain structural units derived from an ethylenically unsaturated monomer having an oxetane group.

When the content of such ethylenically unsaturated monomer (c1) having an oxetane group is 20 to 100% by weight based on the total of all ethylenically unsaturated monomers (c) (100% by weight), excellent crosslinking properties and better resistance and adhesion are obtained. In contrast, when the content of ethylenically unsaturated monomer (c1) having an oxetane group is 0% by weight, crosslinking properties are reduced, resulting in good results in residual film rate, storage stability, and filterability.

Furthermore, the inventors have found through various investigations that the combined use of an acidic resin-type dispersant (C1) in which the content of structural units derived from ethylenically unsaturated monomers having oxetane groups is 20% by mass or more and 100% by mass or less, when the vinyl polymerization portion of the resin-type dispersant is taken as 100% by mass, and an acidic resin-type dispersant (C2) that does not contain structural units derived from ethylenically unsaturated monomers having oxetane groups, results in specifically good results in terms of resistance, adhesion, residual film rate, storage stability, and filterability.

The reason for this unique improvement is believed to be that the resin layer on the colorant particles in the coloring composition exhibits different properties on the surface and inside of the resin layer. Specifically, the molecular weight of ethylenically unsaturated monomers having an oxetane group is often larger than that of other ethylenically unsaturated monomers, and the vinyl polymer portion of the same molecular weight becomes shorter the more ethylenically unsaturated monomers having an oxetane group are contained. Therefore, the acidic resin-type dispersant (C2) that does not contain a structural unit derived from an ethylenically unsaturated monomer having an oxetane group is easily exposed on the surface of the resin layer, and the properties of the acidic dispersant (C2) are dominant with respect to properties that are influenced by the interaction between the particle surface and the outside, such as storage stability and filterability. On the other hand, since the acidic resin-type dispersant (C1) having an oxetane group and the acidic resin-type dispersant (C2) not having an oxetane are mixed inside the resin layer, the crosslinking rate is lower than that of only (C1), which is believed to be the cause of the unique improvement in the remaining film rate. In this invention, the property of the resin layer having different physical properties on the surface and inside, which occurs when two types of resin-type dispersants are used in combination, is called the resin double layer effect.

[Ethylenically unsaturated monomer having an oxetane group (c1)]
Examples of the ethylenically unsaturated monomer (c1) having an oxetane group include (3-ethyloxetan-3-yl)methyl methacrylate.
An example of a commercially available product is ETERNACOLL OXMA ((3-ethyloxetan-3-yl)methyl methacrylate) (manufactured by Ube Industries).

[Ethylenically unsaturated monomer (c2) having no oxetane group]
Examples of ethylenically unsaturated monomers having no oxetane group include the following: By copolymerizing ethylenically unsaturated monomers including an ethylenically unsaturated monomer having a hydroxyl group (c2-1), an ethylenically unsaturated monomer having a t-butyl group (c2-2), and an ethylenically unsaturated monomer having a blocked isocyanate group (c2-3), a thermal crosslinkable group can be introduced into the vinyl polymer portion.
or a hydroxyl group in a hydroxyl group-containing polymer obtained by radical polymerization of an ethylenically unsaturated monomer (c) including an ethylenically unsaturated monomer (c2-1) having a hydroxyl group;
By reacting an isocyanate group with an isocyanate group in the ethylenically unsaturated monomer (c2-4) having a (meth)acryloyl group, a (meth)acryloyl group can be introduced into the vinyl polymer portion.

(Ethylenically unsaturated monomer having a hydroxyl group (c2-1))
The ethylenically unsaturated monomer (c2-1) having a hydroxyl group may be any monomer having a hydroxyl group and an ethylenically unsaturated double bond. Specifically, the ethylenically unsaturated monomer (c2-1) having a hydroxyl group may be a (meth)acrylate monomer having a hydroxyl group, for example, a hydroxyalkyl (meth)acrylate such as 2-hydroxyethyl (meth)acrylate, 2 (or 3)-hydroxypropyl (meth)acrylate, 2 (or 3 or 4)-hydroxybutyl (meth)acrylate, or cyclohexanedimethanol mono(meth)acrylate, or an alkyl-α-hydroxyalkyl acrylate such as ethyl-α-hydroxymethyl acrylate, or a (meth)acrylamide monomer having a hydroxyl group, for example, N-(2-hydroxyethyl)(meth)acrylate, Examples of the monomer include acrylamide, N-(hydroxyalkyl)(meth)acrylamide such as N-(2-hydroxypropyl)(meth)acrylamide and N-(2-hydroxybutyl)(meth)acrylamide, vinyl ether monomers having a hydroxyl group, for example, hydroxyalkyl vinyl ethers such as 2-hydroxyethyl vinyl ether, 2-(or 3-)hydroxypropyl vinyl ether and 2-(or 3- or 4-)hydroxybutyl vinyl ether, and allyl ether monomers having a hydroxyl group, for example, hydroxyalkyl allyl ethers such as 2-hydroxyethyl allyl ether, 2-(or 3-)hydroxypropyl allyl ether and 2-(or 3- or 4-)hydroxybutyl allyl ether.

In addition, ethylenically unsaturated monomers obtained by adding alkylene oxides and/or lactones to the above-mentioned hydroxyalkyl (meth)acrylates, alkyl-α-hydroxyalkyl acrylates, N-(hydroxyalkyl)(meth)acrylamides, hydroxyalkyl vinyl ethers, or hydroxyalkyl allyl ethers can also be used as ethylenically unsaturated monomers having a hydroxyl group in the method of the present invention. As the alkylene oxide to be added, ethylene oxide, propylene oxide, 1,2-, 1,4-, 2,3-, or 1,3-butylene oxide, or a combination of two or more of these can be used. When two or more alkylene oxides are used in combination, the bonding form may be either random and/or block. As the lactone to be added, δ-valerolactone, ε-caprolactone, ε-caprolactone substituted with an alkyl group having 1 to 6 carbon atoms, or a combination of two or more of these can be used. Addition of both alkylene oxides and lactones is also acceptable.

(Ethylenically unsaturated monomer having a t-butyl group (c2-2))
Examples of the ethylenically unsaturated monomer (c2-2) having a t-butyl group include t-butyl methacrylate and t-butyl acrylate.

(Ethylenically unsaturated monomer having a blocked isocyanate group (c2-3)
Examples of the ethylenically unsaturated monomer (c2-3) having a blocked isocyanate group include 2-(0-[1'-methylpropylideneamino]carboxyamino)ethyl methacrylate and 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate.
Examples of commercially available products include Karenz MOI-BM (2-(0-[1'-methylpropylideneamino]carboxyamino)ethyl methacrylate) (manufactured by Showa Denko KK), Karenz MOI-BP (2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate) (manufactured by Showa Denko KK), and the like.

(Ethylenically unsaturated monomer having an isocyanate group and a (meth)acryloyl group (c2-4))
The ethylenically unsaturated monomer (c2-4) having an isocyanate group and a (meth)acryloyl group is a compound having one isocyanate group and one or more (meth)acryloyl groups, preferably a compound having one isocyanate group and one or two (meth)acryloyl groups, and specifically, 2-methacryloyloxyethyl isocyanate, 2-acryloyloxyethyl isocyanate, or 1,1-bis(acryloyloxymethyl)ethyl isocyanate is preferred.
The ethylenically unsaturated monomer (c2-4) having an isocyanate group and a (meth)acryloyl group used in the present invention is not limited to the compounds exemplified above, and may have any structure as long as it has an isocyanate group and one or more (meth)acryloyl groups. These may be used alone or in combination.

[Other ethylenically unsaturated monomers]
In addition to the above-mentioned ethylenically unsaturated monomer (c), for example, alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, trimethylcyclohexyl (meth)acrylate, and isobornyl (meth)acrylate;
Aromatic (meth)acrylates such as phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, and phenoxydiethylene glycol (meth)acrylate;
heterocyclic (meth)acrylates such as tetrahydrofurfuryl (meth)acrylate and oxetane (meth)acrylate;
alkoxypolyalkylene glycol (meth)acrylates such as methoxypolypropylene glycol (meth)acrylate and ethoxypolyethylene glycol (meth)acrylate;
N-substituted (meth)acrylamides such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, and acryloylmorpholine;
Amino group-containing (meth)acrylates such as N,N-dimethylaminoethyl (meth)acrylate and N,N-diethylaminoethyl (meth)acrylate;
and nitriles such as (meth)acrylonitrile. In this specification, (meth)acrylate refers to methacrylate or acrylate, and (meth)acrylamide refers to methacrylamide or acrylamide.

In addition, examples of monomers that can be used in combination with the above acrylic monomers include styrenes such as styrene and α-methylstyrene, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether, and vinyl fatty acid vinyls such as vinyl acetate and vinyl propionate.

[Method for synthesizing dispersant (C)]
Methods for synthesizing the acidic resin-type dispersants (C1) and (C2) include the following synthesis methods (1) to (3), but are not limited thereto.

[Synthesis method (1)]
In the presence of a hydroxyl group-containing compound (a),
a hydroxyl group in a vinyl polymer having two hydroxyl groups at one terminal region, the vinyl polymer being obtained by radical polymerization of an ethylenically unsaturated monomer (c) including at least one selected from the group consisting of an ethylenically unsaturated monomer (c1) having an oxetane group, an ethylenically unsaturated monomer (c2-2) having a t-butyl group, and an ethylenically unsaturated monomer (c2-3) having a blocked isocyanate group;
By reacting with an acid anhydride group in one or more acid anhydrides (b) selected from tetracarboxylic acid anhydrides (b1) and tricarboxylic acid anhydrides (b2), a dispersant having an oxetane group, a t-butyl group, or a blocked isocyanate group as a crosslinkable group can be obtained.

When an ethylenically unsaturated monomer (c2-1) having a hydroxyl group is used in this synthesis method 1, the acid anhydride group in the acid anhydride (b) also reacts with the hydroxyl group of the ethylenically unsaturated monomer (c2-1), which makes it impossible to achieve the objective of reacting with the hydroxyl group at one end of the vinyl polymer, and may result in the desired structure not being obtained, which is undesirable.

[Synthesis method (2)]
In the presence of a compound produced by reacting a hydroxyl group in a hydroxyl group-containing compound (a) with an acid anhydride group in one or more acid anhydrides (b) selected from a tetracarboxylic acid anhydride (b1) and a tricarboxylic acid anhydride (b2),
A dispersant having a hydroxyl group, an oxetane group, a t-butyl group, or a blocked isocyanate group as a crosslinkable group can be obtained by radical polymerization of an ethylenically unsaturated monomer (c) including at least one selected from the group consisting of an ethylenically unsaturated monomer (c1) having an oxetane group having a hydroxyl group, an ethylenically unsaturated monomer (c2-1), an ethylenically unsaturated monomer (c2-2) having a t-butyl group, and an ethylenically unsaturated monomer (c2-3) having a blocked isocyanate group.

The acidic resin-type dispersant (C1) is preferably synthesized by synthesis method (2).

[Synthesis method (3)]
In the presence of a compound produced by reacting a hydroxyl group in a hydroxyl group-containing compound (a) with an acid anhydride group in one or more acid anhydrides (b) selected from a tetracarboxylic acid anhydride (b1) and a tricarboxylic acid anhydride (b2),
A dispersant having a (meth)acryloyl group as a crosslinkable group can be obtained by reacting a hydroxyl group in a hydroxyl group-containing compound obtained by radical polymerization of an ethylenically unsaturated monomer (c) including an ethylenically unsaturated monomer (c2-1) having a hydroxyl group with an isocyanate group in a compound (c2-4) having one isocyanate group and one or more (meth)acryloyl groups.

At this time, the molar ratio of the hydroxyl group in the copolymer after radical polymerization to the isocyanate group in the ethylenically unsaturated monomer (c2-4) having an isocyanate group and a (meth)acryloyl group is preferably 0.2 to 1.0 moles of the isocyanate group in the ethylenically unsaturated monomer (c2-4) having an isocyanate group and a (meth)acryloyl group per mole of the hydroxyl group in the copolymer after radical polymerization, more preferably 0.3 to 1.0 moles, and most preferably 0.5 to 1.0 moles. If it is less than 0.2 moles, the amount of (meth)acryloyl groups will be reduced, resulting in insufficient curability, and if it exceeds 1.0 moles, unreacted isocyanate groups will remain in the resin, resulting in poor storage stability.
The reaction temperature is in the range of 50° C. to 150° C., preferably 70° C. to 120° C. If the reaction temperature is less than 50° C., the reaction rate is slow, whereas if it exceeds 150° C., the urethane group produced by the reaction may decompose.

[Synthesis of polyester moiety]
The synthesis of the polyester portion is a step of reacting an acid anhydride group in one or more acid anhydrides (b) selected from tetracarboxylic acid anhydrides (b1) and tricarboxylic acid anhydrides (b2) with a hydroxyl group in a hydroxyl group-containing compound (a).

(Reaction catalyst)
As the catalyst used in the production of the polyester portion of the present invention, a known catalyst can be used. For example,
Examples of the tertiary amine compounds include triethylamine, triethylenediamine, N,N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo-[5.4.0]-7-undecene, and 1,5-diazabicyclo-[4.3.0]-5-nonene, and mono-n-butyltin(IV) oxide.

(Reaction Solvent)
Although it is possible to produce the polyester portion of the present invention using only the raw materials listed above, it is preferable to use a solvent to avoid problems such as high viscosity and non-uniform reaction. The solvent used is not particularly limited, and any known solvent can be used. Examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, toluene, xylene, and acetonitrile. After the reaction is completed, the solvent used in the reaction can be removed by an operation such as distillation, or can be used as it is as a solvent for the next step or as a part of the product.

(Reaction temperature)
The reaction temperature for the synthesis of the polyester portion is 50° C. to 180° C., preferably in the range of 80° C. to 140° C. If the reaction temperature is below 50° C., the reaction rate is slow, while if it is above 180° C., the carboxyl group and the hydroxyl group undergo an esterification reaction, which may result in a decrease in acid value and gelation. The reaction is ideally stopped by continuing the reaction until the acid anhydride no longer absorbs in infrared absorption, but the reaction may be stopped when 97% or more of the acid anhydride has been half-esterified as determined by acid value measurement.

[Synthesis of vinyl polymer portion]
The vinyl polymer portion in the dispersant (C) is obtained by radical polymerization of an ethylenically unsaturated monomer (c), and has at least one thermally crosslinkable functional group selected from the group consisting of a hydroxyl group, an oxetane group, a t-butyl group, a blocked isocyanate group, and a (meth)acryloyl group. Since this vinyl polymer portion functions as an affinity site for the solvent and the colorant carrier as a side chain of the dispersant (C), the dispersant can have excellent stability even when a fine pigment or a dye is used. In addition, the presence of a thermally crosslinkable group can provide an effect of improving the resistance of the epoxy resin and the coating film.

The content of the ethylenically unsaturated monomer (c) is preferably 3 to 100 parts by weight per part by weight of the hydroxyl group-containing compound (a) and bulk polymerization or solution polymerization is carried out. More preferably, it is 8 to 25 parts by weight, and even more preferably, it is 10 to 20 parts by weight. If it exceeds 100 parts by weight, the molecular weight of the vinyl polymer portion is too high, and the absolute amount of the portion as an affinity portion for the pigment carrier and the solvent increases, and the dispersibility effect itself may decrease. If it is less than 10 parts by weight, the molecular weight of the vinyl polymer portion X is too low, and the steric repulsion effect as an affinity portion for the pigment carrier and the solvent is lost, and it may become difficult to suppress the aggregation of the pigment.

During polymerization, 0.001 to 5 parts by weight of a polymerization initiator can be used based on 100 parts by weight of the ethylenically unsaturated monomer. Azo compounds and organic peroxides can be used as polymerization initiators. Examples of azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane 1-carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2'-azobis(2-methylpropionate), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-hydroxymethylpropionitrile), and 2,2'-azobis[2-(2-imidazolin-2-yl)propane]. Examples of organic peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di(2-ethoxyethyl)peroxydicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxypivalate, (3,5,5-trimethylhexanoyl)peroxide, dipropionyl peroxide, diacetyl peroxide, etc. These polymerization initiators can be used alone or in combination of two or more kinds.

In the case of solution polymerization, the polymerization solvent may be, but is not limited to, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, etc. Two or more of these polymerization solvents may be mixed together.

As the dispersant (X), known techniques such as those described in International Publication No. 2008/007776, JP 2009-155406 A, and JP 2011-157416 A can be used.

Furthermore, in the present invention, the following dispersants may be used.
[Other resin-type dispersants]
Other resin-type dispersants may be any dispersant that has a colorant affinity site that has the property of adsorbing to an added colorant and a site that is compatible with the colorant carrier, and that functions to adsorb to an added colorant and stabilize the dispersion in the colorant carrier. Specific examples of the dispersant that may be used include polyurethane, polycarboxylate esters such as polyacrylate, unsaturated polyamides, polycarboxylates, polycarboxylate (partial) amine salts, polycarboxylate ammonium salts, polycarboxylate alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl-containing polycarboxylate esters, and the like. Examples of the dispersants that can be used include modified polyacrylates, amides formed by the reaction of poly(lower alkylene imine) with a polyester having a free carboxyl group and salts thereof, and other oil-based dispersants; water-soluble resins and water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, and polyvinylpyrrolidone; polyesters, modified polyacrylates, ethylene oxide/propylene oxide adducts, and phosphates. These can be used alone or in combination of two or more.
Examples of polymer dispersants having a basic functional group include nitrogen atom-containing graft copolymers, and nitrogen atom-containing acrylic block copolymers and urethane polymer dispersants having functional groups including tertiary amino groups, quaternary ammonium bases, nitrogen-containing heterocycles, etc. in their side chains.

Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, manufactured by BYK Japan Co., Ltd. 2163, 2164 or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, LPN6919, or Lactimon, Lactimon-WS or Bykumen, etc., SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 260 EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 44 01, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., and Ajispar PA111, PB711, PB821, PB822, PB824, etc. manufactured by Ajinomoto Fine-Techno Co., Ltd.

Furthermore, the content of the resin type dispersant (C1) is preferably 30% by mass or more and less than 70% by mass, based on 100% by mass of the total of the resin type dispersant (C1) and the resin type dispersant (C2), thereby achieving a well-balanced and excellent effect in terms of heat resistance, film remaining rate, and adsorption.
<Binder resin>
In the present invention, a binder resin can be used in combination to impart a function such as developability to the dispersion. The binder resin is a compound necessary for film formation. Examples of the binder resin include thermoplastic resins, thermosetting resins, and active energy ray curable resins having ethylenically unsaturated double bonds. It is also preferable that the active energy ray curable resin has thermosetting properties. From the viewpoint of developability, the binder resin is preferably an alkali-soluble resin.

The content of the binder resin in the coloring composition of the present invention is preferably 20 to 400 parts by mass, and more preferably 50 to 250 parts by mass, per 100 parts by mass of the colorant (A). When an appropriate amount is contained, film formation becomes easy and good color characteristics are easily obtained.

Examples of thermoplastic resins include acrylic resins, butyral resins, styrene-maleic acid copolymers, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl acetate, polyurethane resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins.

Examples of thermosetting resins include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenolic resins.

The binder resin should preferably have a spectral transmittance of 80% or more, and more preferably 95% or more, over the entire wavelength range of 400 to 700 nm in the visible light region.

The alkali-soluble resin is a resin having an acidic group such as a carboxyl group or a sulfonic group. Examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin/maleic acid (anhydride) copolymer, a styrene/styrene sulfonic acid copolymer, an ethylene/(meth)acrylic acid copolymer, or an isobutylene/maleic acid (anhydride) copolymer. Among these, an acrylic resin having an acidic group and a styrene/styrene sulfonic acid copolymer, which have improved heat resistance and transparency, are preferred, and an acrylic resin having an acidic group is more preferred.

To impart photoreactivity to the alkali-soluble resin, it is preferable to use an active energy ray-curable resin having an ethylenically unsaturated active double bond. This improves the solvent resistance of the cured coating.

Examples of active energy ray-curable resins having ethylenically unsaturated double bonds include resins into which unsaturated ethylenically double bonds have been introduced by the following methods (a) to (c).

[Method (a)]
Method (a) can be exemplified by a method in which an unsaturated ethylenic monomer having an epoxy group is copolymerized with one or more other monomers to obtain a copolymer, and a carboxyl group of an unsaturated monobasic acid having an unsaturated ethylenic double bond is subjected to an addition reaction with the side-chain epoxy group of the copolymer, and then a polybasic acid anhydride is reacted with the resulting hydroxyl group to introduce an unsaturated ethylenic double bond and a carboxyl group.

Examples of unsaturated ethylenic monomers having an epoxy group include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4 epoxybutyl (meth)acrylate, and 3,4 epoxycyclohexyl (meth)acrylate, which may be used alone or in combination of two or more. Glycidyl (meth)acrylate is preferred from the viewpoint of reactivity with the unsaturated monobasic acid in the next step.

Examples of unsaturated monobasic acids include monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid, and (meth)acrylic acid substituted with haloalkyl, alkoxyl, halogen, nitro, or cyano at the α-position. These may be used alone or in combination of two or more.

Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc., which may be used alone or in combination of two or more. If necessary, for example to increase the number of carboxyl groups, it is also possible to use a tricarboxylic acid anhydride such as trimellitic anhydride, or a tetracarboxylic acid dianhydride such as pyromellitic dianhydride to hydrolyze the remaining anhydride groups. In addition, if tetrahydrophthalic anhydride or maleic anhydride, which has an unsaturated ethylenic double bond, is used as the polybasic acid anhydride, the number of unsaturated ethylenic double bonds can be further increased.

[Method (b)]
As a method similar to the method (a), for example, there is a method in which an unsaturated ethylenic monomer having an epoxy group is added to a part of the side chain carboxyl groups of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having a carboxyl group with one or more other monomers, thereby introducing an unsaturated ethylenic double bond and a carboxyl group.
In this method, a larger amount of hydroxyl groups derived from the unsaturated ethylenic monomer having an epoxy group is generated compared to the method (a). When the resin having a cationic group in the side chain used for obtaining the salt forming compound of the present invention contains an oxetanyl group or a t-butyl group as a thermally crosslinkable functional group, it is preferable to use the resin obtained by the method (b) as the binder resin because it exhibits higher heat resistance.

[Method (c)]
Method (c) includes a method in which an unsaturated ethylenic monomer having a hydroxyl group is used and copolymerized with another monomer of an unsaturated monobasic acid having a carboxyl group or with another monomer, and the side chain hydroxyl group of the copolymer is reacted with an isocyanate group of an unsaturated ethylenic monomer having an isocyanate group.

The unsaturated ethylenic monomer having a hydroxyl group includes hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2-, 3- or 4-hydroxybutyl (meth)acrylate, glycerol (meth)acrylate, or cyclohexanedimethanol mono(meth)acrylate, which may be used alone or in combination of two or more. In addition, polyether mono(meth)acrylates obtained by addition polymerization of ethylene oxide, propylene oxide, and/or butylene oxide to the above hydroxyalkyl (meth)acrylates, and (poly)ester mono(meth)acrylates obtained by addition of (poly)γ-valerolactone, (poly)ε-caprolactone, and/or (poly)12-hydroxystearic acid, etc., may also be used. From the viewpoint of suppressing foreign matter in the coating, 2-hydroxyethyl (meth)acrylate or glycerol (meth)acrylate is preferred.

Examples of unsaturated ethylenic monomers having an isocyanate group include 2-(meth)acryloyloxyethyl isocyanate and 1,1-bis[(meth)acryloyloxy]ethyl isocyanate, but are not limited to these and two or more types can be used in combination.

From the viewpoint of film-forming properties and coating resistance, the weight average molecular weight (Mw) of the binder resin is preferably in the range of 10,000 to 100,000, and more preferably in the range of 10,000 to 80,000. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw/Mn is preferably 10 or less.

When the binder resin is used as a photosensitive composition, it is preferable to use a resin with an acid value of 20 to 300 mgKOH/g from the viewpoints of dispersibility, penetration, developability, and heat resistance of the pigment and salt-forming compound. If the acid value is less than 20 mgKOH/g, the solubility in the developer is poor, making it difficult to form a fine pattern. If the acid value exceeds 300 mgKOH/g, the fine pattern may not remain.

The binder resin is preferably used in an amount of 30 parts by mass or more per 100 parts by mass of colorant (A) because of its good film-forming properties and various resistances, and is preferably used in an amount of 500 parts by mass or less because the colorant concentration is high and good color characteristics can be expressed.

(Thermosetting Compound)
In the present invention, a thermosetting compound may be further contained in combination with the thermoplastic resin, which is the binder resin. Examples of the thermosetting compound include epoxy compounds and/or resins, oxetane compounds and/or resins, benzoguanamine compounds and/or resins, rosin-modified maleic acid compounds and/or resins, rosin-modified fumaric acid compounds and/or resins, melamine compounds and/or resins, urea compounds and/or resins, and phenol compounds and/or resins.

<Organic Solvent>
The organic solvent is used to assist the dispersion of the colorant and to appropriately adjust the viscosity of the coloring composition.

Examples of organic solvents include ethyl lactate, benzyl alcohol, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, and n-butylbenzene. , n-propyl acetate, o-xylene, o-diethylbenzene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alkoxide Cole, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid esters, etc.

Among these, it is preferable to use glycol acetates such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate, alcohols such as benzyl alcohol, diacetone alcohol, and 3-methoxybutanol, and ketones such as cyclohexanone, because these have good dispersibility and penetration of the colorant and good applicability of the coloring composition.

Organic solvents can be used alone or in combination of two or more types.

The organic solvent is preferably used in an amount of 500 to 4,000 parts by mass per 100 parts by mass of colorant (A), since it adjusts the viscosity of the coloring composition to an appropriate level and enables the formation of a colored film with the desired uniform thickness.

<Polymerizable monomer>
The coloring composition of the present invention can be used as a photosensitive coloring composition by further adding a polymerizable monomer and/or a photopolymerization initiator. The polymerizable monomer that may be added to the coloring composition of the present invention includes a monomer or oligomer that is cured by ultraviolet light, heat, or the like to form a transparent resin.

Examples of monomers and oligomers that harden when exposed to ultraviolet light or heat to produce a transparent resin include methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, and bisphenol A diglycidyl. Examples of the acrylates include, but are not limited to, ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl (meth)acrylate, ester acrylate, (meth)acrylic acid ester of methylol melamine, epoxy (meth)acrylate, urethane acrylate, and various other acrylates and methacrylates, (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinyl formamide, and acrylonitrile.

The polymerizable compounds can be used alone or in combination of two or more types.

The content of the polymerizable monomer is preferably 5 to 400 parts by mass, and more preferably 10 to 300 parts by mass, per 100 parts by mass of colorant (A). When an appropriate amount is added, the photocurability and developability are further improved.

<Photopolymerization initiator>
The coloring composition of the present invention may contain a photopolymerization initiator. This facilitates photocuring when forming a filter segment by photolithography. The amount of the photopolymerization initiator is preferably 5 to 200 mass%, more preferably 10 to 150 mass%, based on 100 parts by mass of the coloring agent (A). When an appropriate amount is added, the photocurability and developability are further improved.

The photopolymerization initiator is, for example, an acetophenone-based compound such as 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, or 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin compounds such as benzoylbenzoic acid, benzoylbenzoic acid methyl, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, and 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; thioxanthone compounds such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, and 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine. , 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine; triazine-based compounds such as 1-(N-4-benzoylphenyl-carbazol-3-yl)- Oxime ester compounds such as butane-1,2-dione-2-oxime-O-acetate, 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), or O-(acetyl)-N-(1-phenyl-2-oxo-2-(4'-methoxy-naphthyl)ethylidene)hydroxylamine; phosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; Borate-based compounds; carbazole-based compounds; imidazole-based compounds; or titanocene-based compounds, etc., are used.

Photopolymerization initiators can be used alone or in combination of two or more types.

The content of the photopolymerization initiator is preferably 5 to 200% by mass, and more preferably 10 to 150% by mass, relative to 100 parts by mass of colorant (A). When an appropriate amount is used, the photocuring property and developability are further improved.

<Sensitizer>
In the coloring composition of the present invention, a photopolymerization initiator and a sensitizer can be used in combination.
Examples of the sensitizer include polymethine dyes such as chalcone derivatives, unsaturated ketones typified by dibenzalacetone, 1,2-diketone derivatives typified by benzil and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, and oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triphenylmethane derivatives, tetrabenzoporphyrin derivatives, and tetrapyrazinoporphyrazine derivatives. Examples of such compounds include compounds having the formula (I)-1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 112, 123, 134, 140, 155, 165, 170, 186, 197, 198, 199, 200, 213, 220, 234, 240, 256, 261, 270, 281, 2

Further examples include sensitizers described in "Dye Handbook" edited by Makoto Okawara et al. (Kodansha, 1986), "Chemistry of Functional Dyes" edited by Makoto Okawara et al. (CMC, 1981), and "Special Functional Materials" edited by Chuzo Ikemori et al. (CMC, 1986).

Sensitizers can be used alone or in combination of two or more types.

The amount of sensitizer used is preferably 3 to 60% by weight, more preferably 5 to 50% by weight, based on 100 parts by weight of the photopolymerization initiator. Using an appropriate amount will further improve photocurability and developability.

<Amine compounds>
The coloring composition of the present invention may contain an amine compound. The amine compound is capable of reducing dissolved oxygen.

Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, and N,N-dimethyl-p-toluidine.

<Leveling Agent>
The coloring composition of the present invention may contain a leveling agent, which improves the coatability and the surface smoothness of the coating film.
Examples of the leveling agent include, in addition to dimethylsiloxane, various surfactants such as silicone surfactants, fluorine surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants.
The dimethylsiloxane is preferably a dimethylsiloxane having a polyether structure and/or a polyester structure in the main chain. Commercially available products of dimethylsiloxane having a polyether structure in the main chain include FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, and FZ-2207 manufactured by Dow Corning Toray Co., Ltd., and BYK-333 manufactured by BYK-Chemie Co., Ltd. Commercially available products of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK-Chemie Co., Ltd.

Anionic surfactants include polyoxyethylene alkyl ether sulfates, sodium dodecylbenzene sulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkyl naphthalene sulfonates, sodium alkyl diphenyl ether disulfonates, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine styrene-acrylic acid copolymers, polyoxyethylene alkyl ether phosphates, etc.

Cationic surfactants include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants that are added supplementarily to the leveling agent include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate esters, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate, etc.; alkyl betaines such as alkyl dimethylamino acetate betaine, amphoteric surfactants such as alkyl imidazolines, and fluorine-based and silicone-based surfactants.

Leveling agents can be used alone or in combination of two or more types.

The content of the leveling agent is preferably 0.003 to 0.5% by mass in 100% by mass of the coloring composition.

<Epoxy Compound>
The coloring composition of the present invention can contain an epoxy compound.

Examples of epoxy compounds include phenol novolac type epoxy resins, cresol novolac type epoxy resins, trishydroxyphenylmethane type epoxy resins, dicyclopentadiene phenol type epoxy resins, bisphenol-A type epoxy resins, bisphenol-F type epoxy resins, biphenol type epoxy resins, bisphenol-A novolac type epoxy resins, naphthalene skeleton-containing epoxy resins, alicyclic epoxy resins, and heterocyclic epoxy resins.

Commercially available phenol novolac epoxy resins include, for example, Epicron N-740, Epicron N-770, and Epicron N-775 manufactured by DIC Corporation, D.E. N438 manufactured by Dow Chemical Company, RE-306 manufactured by Nippon Kayaku Co., Ltd., and jER152 and jER154 manufactured by Mitsubishi Chemical Corporation.

Commercially available cresol novolac epoxy resins include Epicron N-660, Epicron N-665, Epicron N-670, Epicron N-673, Epicron N-680, Epicron N-695, Epicron N-665-EXP, and Epicron N-672-EXP manufactured by DIC Corporation, EOCN-102S, EOCN-103S, and EOCN-104S manufactured by Nippon Kayaku Co., Ltd., UVR-6650 manufactured by Union Carbide Corporation, and ESCN-195 manufactured by Sumitomo Chemical Co., Ltd.

Commercially available trishydroxyphenylmethane epoxy resins include EPPN-503, EPPN-502H, and EPPN-501H manufactured by Nippon Kayaku Co., Ltd., TACTIX-742 manufactured by Dow Chemical Co., and jER E1032H60 manufactured by Mitsubishi Chemical Corporation.

Commercially available dicyclopentadiene phenol type epoxy resins include Epicron EXA-7200 manufactured by DIC Corporation and TACTIX-556 manufactured by Dow Chemical Company.

Commercially available bisphenol-type epoxy resins include bisphenol-A type epoxy resins such as jER828 and jER1001 manufactured by Mitsubishi Chemical Corporation, UVR-6410 manufactured by Union Carbide Corporation, D.E.R-331 manufactured by Dow Chemical Company, and YD-8125 manufactured by Shin-Nihon Kagaku Epoxy Manufacturing Co., Ltd., and bisphenol-F type epoxy resins such as UVR-6490 manufactured by Union Carbide Corporation and YDF-8170 manufactured by Shin-Nihon Kagaku Epoxy Manufacturing Co., Ltd.

Commercially available biphenol-type epoxy resins include biphenol-type epoxy resins such as NC-3000 and NC-3000H manufactured by Nippon Kayaku Co., Ltd., and bixylenol-type epoxy resins such as jER YX-4000 and jER YL-6121 manufactured by Mitsubishi Chemical Corporation.

Commercially available bisphenol A novolac epoxy resins include Epicron N-880 manufactured by DIC Corporation and jER E157S75 manufactured by Mitsubishi Chemical Corporation.

Commercially available naphthalene skeleton-containing epoxy resins include NC-7000 and NC-7300 manufactured by Nippon Kayaku Co., Ltd., and EXA-4750 manufactured by DIC Corporation.

Commercially available alicyclic epoxy resins include Seikicide 2021P, 2081, 2000, Epolead PB3600, PB4700, GT401, EHPE-3150, and Cyclomer M100 manufactured by Daicel Corporation.

Commercially available heterocyclic epoxy resins include TEPIC-L, TEPIC-H, and TEPIC-S manufactured by Nissan Chemical Industries, Ltd.

Epoxy compounds can be used alone or in combination of two or more types.

The content of the epoxy compound is preferably 0.5 to 50% by mass, and more preferably 1 to 40% by mass, based on 100% by mass of the non-volatile content of the coloring composition. When an appropriate amount is contained, heat resistance is further improved.

<Oxetane Compound>
The coloring composition of the present invention may contain an oxetane compound. Examples of the oxetane compound include compounds having monofunctional, difunctional, and trifunctional or higher oxetane groups.

Examples of compounds with a monofunctional oxetane group include (3-ethyloxetan-3-yl)methyl acrylate, (3-ethyloxetan-3-yl)methyl methacrylate, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-(2-methacryloxymethyl)oxetane, and 3-ethyl-3-{[3-(triethoxysilyl)propoxy]methyl}oxetane. Commercially available products include OXE-10 and OXE-30 manufactured by Osaka Organic Chemical Industry Co., Ltd., and OXT-101 and 212 manufactured by Toagosei Co., Ltd.

Examples of compounds with bifunctional oxetane groups include 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl), 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, di[1-ethyl(3-oxetanyl)]methyl ether, and di[1-ethyl(3-oxetanyl)]methyl ether-3-ethyl-3-hydroxymethyloxetane. , 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(2-phenoxymethyl)oxetane, 3,7-bis(3-oxetanyl)-5-oxa-nonane, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycose bis(3-ethyl-3-oxetanylmethyl)ether, dicyclopentenyl bis(3-ethyl 1,4-bis(3-ethyl-3-oxetanylmethyl)ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, tetraethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, polyethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, ethylene oxide (EO) modified Examples of such products include bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, propylene oxide (PO)-modified bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, EO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, PO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, and EO-modified bisphenol F (3-ethyl-3-oxetanylmethyl)ether. Commercially available products include OXBP and OXTP manufactured by Ube Industries, and OXT-121 and OXT-221 manufactured by Toagosei.

Examples of compounds with three or more functional oxetane groups include pentaerythritol tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, and caprolactone-modified dipentaerythritol. Examples include taerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis(3-ethyl-3-oxetanylmethyl) ether, resins containing oxetane groups (such as the oxetane-modified phenol novolac resin described in Japanese Patent No. 3783462), and polymers obtained by radical polymerization of (meth)acrylic monomers such as the aforementioned OXE-30.

Oxetane compounds can be used alone or in combination of two or more types.

The content of the oxetane compound is preferably 0.5 to 50% by mass, and more preferably 1 to 40% by mass, based on 100% by mass of the non-volatile content of the coloring composition. When an appropriate amount is contained, heat resistance is further improved.

<Curing agent, curing accelerator>
The colored composition of the present invention may contain a curing agent and a curing accelerator to assist the curing of the thermosetting resin.
Examples of the curing agent include phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds, etc. Among these, compounds having two or more phenolic hydroxyl groups in one molecule and amine curing agents are preferred.
Examples of the curing accelerator include amine compounds (e.g., dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (e.g., triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (e.g., dimethylamine, etc.), imidazole derivatives, bicyclic amidine compounds and their salts (e.g., imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, etc.), and the like. imidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, etc.), phosphorus compounds (for example, triphenylphosphine, etc.), guanamine compounds (for example, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (for example, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine·isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine·isocyanuric acid adduct, etc.).

The hardener and hardening accelerator can be used alone or in combination of two or more types.

The amount of the curing agent and curing accelerator used is preferably 0.01 to 15 mass% per 100 mass parts of the thermosetting resin.

<Ultraviolet absorbing agent>
The coloring composition of the present invention may contain an ultraviolet absorbing agent. Examples of the ultraviolet absorbing agent include benzotriazole-based organic compounds, triazine-based organic compounds, benzophenone-based organic compounds, cyanoacrylate-based organic compounds, and salicylate-based organic compounds.

The content of the ultraviolet absorber is preferably 5 to 70% by mass, with the total of the photopolymerization initiator and the ultraviolet absorber being 100% by mass. This allows a high degree of compatibility between photosensitivity and resolution. Note that when the coloring composition contains a sensitizer, the content of the photopolymerization initiator includes the content of the sensitizer.

The total content of the photopolymerization initiator and the UV absorber is preferably 1 to 20% by mass, based on 100% by mass of the non-volatile content of the photosensitive coloring composition. If the total content of the photopolymerization initiator and the UV absorber is less than the above, adhesion may weaken and pixel peeling may occur, and if it is more than the above, the sensitivity may be too high, resulting in poor resolution.

Examples of benzotriazole-based organic compounds include 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, a mixture of octyl-3[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate and 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate, 2-[2-hydroxy-3,5-bis(α, α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-(1,1-dimethylethyl)-4-hydroxy, C7-9 side chain and straight chain alkyl ester compound, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol.

Commercially available products include BASF's "TINUVIN P", "TINUVIN PS", "TINUVIN 109", "TINUVIN 234", "TINUVIN 326", "TINUVIN 328", "TINUVIN 329", "TINUVIN 360", "TINUVIN 384-2", "TINUVIN 900", "TINUVIN 928", "TINUVIN 99-2", and "TINUVIN 1130", ADEKA's "ADEKA STAB LA-29", and Otsuka Chemical's "RUNA-93".

Examples of triazine-based organic compounds include 2-[4,6-di(2,4-xylyl)-1,3,5-triazin-2-yl]-5-octyloxyphenol, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, reaction product of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl-glycidic acid ester, 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3-5-triazine, etc.

Commercially available products include "KEMISORB 102" manufactured by Chemipro Chemicals, "TINUVIN 400", "TINUVIN 405", "TINUVIN 460", "TINUVIN 477-DW", "TINUVIN 479", and "TINUVIN 1577" manufactured by BASF, "ADEKA STAB LA-46" and "ADEKA STAB LA-F70" manufactured by ADEKA, and "CYASORB UV-1164" manufactured by Sun Chemical.

Examples of benzophenone-based organic compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid-3H2O, 2-hydroxy-4-n-octoxybenzophenone, and 2,2-dihydroxy-4-methoxybenzophenone.

Commercially available products include "KEMISORB 10," "KEMISORB 11," "KEMISORB 11S," "KEMISORB 12," and "KEMISORB 111" manufactured by Chemipro Chemicals, "SEESORB 101" and "SEESORB 107" manufactured by Shipro Chemicals, and "ADEKA STAB 1413" manufactured by ADEKA Corporation.

<Thiol-based chain transfer agent>
The coloring composition can contain a thiol-based chain transfer agent. When the thiol-based chain transfer agent is used together with a photopolymerization initiator, it acts as a chain transfer agent in the radical polymerization process after light irradiation, and generates thiyl radicals that are not easily inhibited by oxygen, thereby improving the photosensitivity. This further improves the photocurability from the surface of the coating to the depth of the coating.

Multifunctional thiols include, for example, hexanedithiol and decanedithiol. , 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid tris(2-hydroxyethyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine, etc. are included, and preferably, ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate are included.

Thiol-based chain transfer agents can be used alone or in combination of two or more types.

The content of the thiol chain transfer agent is preferably 1 to 10%, and more preferably 2 to 8%, based on 100% by mass of the non-volatile content of the coloring composition. When used in an appropriate amount, the photosensitivity is improved and a coating with a good shape can be obtained.

<Antioxidants>
The coloring composition of the present invention can contain an antioxidant. The antioxidant can suppress the coating film formed from the coloring composition from oxidizing and yellowing due to a heating process such as thermal curing, and can maintain the transmittance of the coating film. In particular, when the colorant concentration of the photosensitive coloring composition is high, the crosslinking component is relatively reduced, and therefore, if a highly sensitive crosslinking component is used or the amount of the photopolymerization initiator is increased, the yellowing during the heating process becomes stronger. Therefore, by including an antioxidant, yellowing due to oxidation during the heating process can be prevented, and a high transmittance of the coating film can be obtained.

The "antioxidant" in the present invention may be any compound that has an ultraviolet absorbing function, a radical scavenging function, or a peroxide decomposing function. Specific examples of the antioxidant include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylic acid ester-based, and triazine-based compounds, and known ultraviolet absorbers, antioxidants, etc. can be used. In addition, it is preferable that the antioxidant used in the present invention does not contain a halogen atom.

Among these antioxidants, from the viewpoint of achieving both the transmittance and sensitivity of the coating film, preferred ones include hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants.

Examples of hindered phenol-based antioxidants include 2,4-bis[(laurylthio)methyl]-o-cresol, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,6-di-t-butyl-4-nonylphenol, 2,2'-isobutylidene-bis-(4,6-dimethyl-phenol), 4,4'-butyl Examples of the phenol include 2,2'-thiodiethyl bis-(2-t-butyl-5-methylphenol), 2,2'-thio-bis-(6-t-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,2'-thiodiethyl bis-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate, 1,1,3-tris-(2'-methyl-4'-hydroxy-5'-t-butylphenyl)-butane, 2,2'-methylene-bis-(6-(1-methyl-cyclohexyl)-p-cresol), 2,4-dimethyl-6-(1-methyl-cyclohexyl)-phenol, and N,N-hexamethylene bis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide). In addition, oligomer and polymer type compounds having a hindered phenol structure can also be used.
Commercially available products include Adeka STAB AO-20, AO-30, AO-40, AO50, AO60, AO80, and AO320 manufactured by ADEKA CORPORATION; KEMINOX 101, 179, 76, and 9425 manufactured by Chemipro Corporation; IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, and 565 manufactured by BASF Corporation; and Cyanox CY-1790 and CY-2777 manufactured by Sun Chemical Company.

Examples of the hindered amine antioxidant include bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(N-methyl-2,2,6,6-tetramethyl-4-piperidyl)sebacate, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexamethylenediamine, and 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino. -N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)(1,2,3,4-butanetetracarboxylate, poly[{6-(1,1,3,3-tetramethylbutyl)imino-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidyl)imino}hexamethyl {(2,2,6,6-tetramethyl-4-piperidyl)imino}], poly[(6-morpholino-1,3,5-triazine-2,4-diyl){(2,2,6,6-tetramethyl-4-piperidyl)imino}hexamethine{(2,2,6,6-tetramethyl-4-piperidyl)imino}], polycondensate of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, N,N'-4,7-tetrakis[4,6-bis{N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino}-1,3,5-triazine-2-yl]-4,7-diazadecane-1,10-diamine, etc. In addition, oligomer type and polymer type compounds having a hindered amine structure can also be used.
Commercially available products include Adeka STAB LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87, LA-402F, and LA-502XP manufactured by ADEKA CORPORATION; KAMISTAB 29, 62, 77, 29, and 94 manufactured by Chemipro Chemicals; Tinuvin 249, TINUVIN 111FDL, 123, 144, 292, and 5100 manufactured by BASF Corporation; and Cyasorb UV-3346, UV-3529, and UV-3853 manufactured by Sun Chemical Co., Ltd.

Examples of phosphorus-based antioxidants include tris(isodecyl)phosphite, tris(tridecyl)phosphite, phenyl isooctyl phosphite, phenyl isodecyl phosphite, phenyl di(tridecyl)phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl phosphite, diphenyl tridecyl phosphite, triphenyl phosphite, tris(nonylphenyl)phosphite, 4,4'isopropylidenediphenol alkyl phosphite, trisnonylphenyl phosphite, tris(2,4-di-t-butylphenyl)phosphite, tris(biphenyl)phosphite, distearyl pentaerythritol diphosphite, di(2,4-di-t-butylphenyl)pentaerythritol Examples of suitable phosphite include tetratridecyl 4,4'-butylidene bis(3-methyl-6-t-butylphenol) diphosphite, hexatridecyl 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl) butane triphosphite, 3,5-di-t-butyl-4-hydroxybenzyl phosphite diethyl ester, sodium bis(4-t-butylphenyl) phosphite, sodium-2,2-methylene-bis(4,6-di-t-butylphenyl)-phosphite, 1,3-bis(diphenoxyphosphonyloxy)-benzene, and ethyl bis(2,4-ditert-butyl-6-methylphenyl) phosphite. In addition, oligomer-type and polymer-type compounds having a phosphite structure can also be used.
Commercially available products include Adeka STAB PEP-36, PEP-8, HP-10, Adeka STAB 2112, 1178, 1500, C, 3013, and TPP manufactured by ADEKA CORPORATION, IRGAFOS168 manufactured by BASF Corporation, and HostanoxP-EPQ manufactured by Clariant Chemicals.

Examples of sulfur-based antioxidants include 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis[(octylthio)methyl]-o-cresol, 2,4-bis[(laurylthio)methyl]-o-cresol, 2,2-bis{[3-(dodecylthio)-1-oxopropoxy]methyl}propane-1,3-diylbis[3-(dodecylthio)propionate], 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], etc. In addition, oligomer-type and polymer-type compounds having a thioether structure can also be used.
Examples of commercially available products include Adeka STAB AO-412S and AO-503 manufactured by ADEKA CORPORATION, and KEMINOX PLS manufactured by Chemipro Chemicals Co., Ltd.

As the benzotriazole-based antioxidant, oligomer-type and polymer-type compounds having a benzotriazole structure can be used.
Commercially available products include Adeka STAB LA-29, LA-31RG, LA-32, LA-36, -412S manufactured by ADEKA CORPORATION, KEMISORB71, 73, 74, 79, 279 manufactured by Chemipro Chemicals Co., Ltd., and TINUVIN PS, 99-2, 384-2, 900, 928, 1130 manufactured by BASF Corporation.

Benzophenone-based antioxidants include 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'dihydroxy-4-methoxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, etc. In addition, oligomer-type and polymer-type compounds having a benzophenone structure can also be used.
Examples of commercially available products include Adeka STAB 1413 manufactured by ADEKA CORPORATION, KEMISORB 10, 11, 11S, 12, and 111 manufactured by Chemipro Chemicals Co., Ltd., and UV-12 and UV-329 manufactured by Sun Chemical Co., Ltd.

Examples of triazine-based antioxidants include 2,4-bis(allyl)-6-(2-hydroxyphenyl)1,3,5-triazine, etc. In addition, oligomer-type and polymer-type compounds having a triazine structure can also be used.
Examples of commercially available products include Adeka STAB LA-46 and F70 manufactured by ADEKA CORPORATION, KEMISORB102 manufactured by Chemipro Chemicals, TINUVIN 400, 405, 460, 477, and 479 manufactured by BASF Corporation, and Cyasorb UV-1164 manufactured by Sun Chemical Company.

Examples of salicylic acid ester antioxidants include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate. Other oligomer and polymer type compounds having a salicylic acid ester structure can also be used.

These antioxidants can be used alone or in a mixture of two or more in any ratio as needed.

In addition, it is more preferable that the content of the antioxidant is 0.5 to 5.0% by mass based on 100% by mass of the non-volatile content of the coloring composition, since this leads to good spectral characteristics and sensitivity.

<Other additives>
The colored composition of the present invention may contain, as other additives, a storage stabilizer for stabilizing the viscosity of the composition over time, and an adhesion improver such as a silane coupling agent for improving adhesion to a transparent substrate.

Examples of storage stabilizers include quaternary ammonium chlorides such as benzyl trimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, t-butylpyrocatechol, organic phosphines such as tetraethylphosphine and tetraphenylphosphine, and phosphites. The amount of storage stabilizer used is preferably 0.1 to 10 parts by mass per 100 parts by mass of colorant.

Adhesion improvers include vinyl silanes such as vinyltris(β-methoxyethoxy)silane, vinylethoxysilane, and vinyltrimethoxysilane, (meth)acrylic silanes such as γ-methacryloxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)methyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-epoxycyclohexyl)methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropyltriethoxysilane. Examples of the silane coupling agents include epoxy silanes such as N-β(aminoethyl)γ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropyltriethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The amount of the adhesion improver used is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5% by mass, relative to 100 parts by mass of the colorant.

<Method of producing colored composition>
The coloring composition of the present invention is preferably produced by finely dispersing a mixture containing a colorant (A), a dye derivative (B), a resin-type dispersant (C), and an organic solvent using various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, a kneader, or an attritor. The coloring composition of the present invention can also be produced by dispersing the colorant (A) separately and then mixing them. When the solubility of the colorant, such as a dye, is high, specifically, when the solubility in the solvent used is high and the colorant is dissolved by stirring and no foreign matter is found, the above-mentioned fine dispersion step does not need to be performed. In addition, when the mixture contains a pigment, it is preferable to use a dispersing aid such as a dye derivative in combination.

When used as a photosensitive coloring composition, it is preferable to prepare it as a solvent-developable or alkali-developable composition. The photosensitive coloring composition can be prepared by mixing the coloring composition, a photopolymerization monomer and/or a photopolymerization initiator, and, if necessary, a solvent, other dispersing aids, and additives. The photopolymerization initiator may be added at the stage of preparing the coloring composition, or may be added later to the prepared coloring composition.

When dispersing the colorant (A), a dispersing aid (e.g., a surfactant) or the like can be used as appropriate. Dispersing aids are excellent at dispersing the colorant and have a large effect of preventing the colorant from re-aggregating after dispersion, so that high transmittance can be obtained.

<Dispersion Aid>
(Surfactant)
Examples of the surfactant include anionic surfactants such as sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salts of styrene-acrylic acid copolymers, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymers, and polyoxyethylene alkyl ether phosphates; nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphates, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; cationic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyl betaines such as alkyl dimethylaminoacetate betaine, and amphoteric surfactants such as alkyl imidazolines. These can be used alone or in a mixture of two or more, but are not necessarily limited to these.

Dispersing agents can be used alone or in combination of two or more types.

The amount of dispersing agent used is preferably 0.1 to 55 parts by weight, more preferably 0.1 to 45 parts by weight, per 100 parts by weight of colorant. Using an appropriate amount will further improve dispersibility.

<Removal of coarse particles>
The coloring composition of the present invention is preferably subjected to removal of coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more, and mixed dust by means of centrifugation, filtration with a sintered filter or a membrane filter, etc. In this way, it is preferable that the coloring composition does not substantially contain particles of 0.5 μm or more. More preferably, the particles are 0.3 μm or less.

<Color filter>
One embodiment of the present invention relates to a color filter. The color filter includes a filter segment formed from the photosensitive coloring composition on a substrate.

The color filter of one embodiment is described below.

[Color filter manufacturing method]
The color filter of the present invention can be manufactured by a printing method or a photolithography method. The formation of filter segments by a printing method can be patterned by simply repeating printing and drying of a colored composition prepared as a printing ink, and is therefore a low-cost and mass-productive manufacturing method for color filters. Furthermore, the development of printing technology has made it possible to print fine patterns with high dimensional accuracy and smoothness. In order to perform printing, it is preferable to use a composition that does not allow the ink to dry or solidify on the printing plate or blanket. In addition, control of the fluidity of the ink on the printing machine is also important, and the ink viscosity can be adjusted by using a dispersant or an extender pigment.

When forming a filter segment by photolithography, a photosensitive coloring composition prepared as an organic solvent development type or an alkali development type is applied to a transparent substrate by a coating method such as spray coating, spin coating, slit coating, or roll coating so that the dry film thickness is 0.2 to 5 μm. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern that is in contact with or not in contact with the film. Thereafter, the uncured parts are removed by immersing the film in an organic solvent or an alkali developer or spraying the developer by a spray or the like to form a desired pattern, and the same operation is repeated for other colors to produce a color filter. Furthermore, heating can be performed as necessary to promote polymerization of the photosensitive coloring composition. According to the photolithography method, a color filter with higher accuracy than the above-mentioned printing method can be produced.

In the development, an aqueous solution of sodium carbonate, sodium hydroxide, or the like is used as an alkaline developer, and an organic alkali such as dimethylbenzylamine, triethanolamine, etc. may also be used. The developer may also contain an antifoaming agent or a surfactant.
In order to increase the exposure sensitivity, after the photosensitive coloring composition is coated and dried, a water-soluble or alkaline water-soluble resin, such as polyvinyl alcohol or a water-soluble acrylic resin, may be coated and dried to form a film that prevents polymerization inhibition due to oxygen, and then ultraviolet exposure may be performed.

The color filter of the present invention can be manufactured by the above-mentioned method, as well as by the electrodeposition method, transfer method, inkjet method, etc., and the photosensitive coloring composition of the present invention can be used for any of these methods. The electrodeposition method is a method of manufacturing a color filter by using a transparent conductive film formed on a substrate to electrodeposit each color filter segment onto the transparent conductive film by electrophoresis of colloidal particles. The transfer method is a method in which filter segments are formed in advance on the surface of a peelable transfer base sheet, and the filter segments are then transferred to the desired substrate.

Before forming the filter segments on a base material such as a transparent substrate or a reflective substrate, a black matrix can be formed in advance. Examples of the black matrix include, but are not limited to, a multilayer film of chromium or chromium/chromium oxide, an inorganic film such as titanium nitride, or a resin film with a light-shielding agent dispersed therein. Thin film transistors (TFTs) can also be formed in advance on the transparent substrate or reflective substrate, and then each color filter segment can be formed. In addition, an overcoat film, a transparent conductive film, etc. can be formed on the color filter of the present invention as necessary.

The dry film thickness of the filter segments and black matrix is preferably 0.2 to 10 μm, and more preferably 0.2 to 5 μm. When drying the coating film, a vacuum dryer, convection oven, IR oven, hot plate, etc. may be used.

The color filter is attached to the opposing substrate using a sealant, liquid crystal is injected through an injection port provided in the seal, the injection port is then sealed, and a polarizing film or retardation film is attached to the outside of the substrate as required, to produce a liquid crystal display panel.

Such liquid crystal display panels can be used in liquid crystal display modes that use color filters such as twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically concentric bend (OCB).

Transparent substrates include glass plates such as soda-lime glass, low-alkali borosilicate glass, and non-alkali aluminoborosilicate glass, and resin plates such as polycarbonate, polymethylmethacrylate, and polyethylene terephthalate. Transparent electrodes made of indium oxide, tin oxide, etc. may be formed on the surface of the glass or resin plate to drive the liquid crystal after panelization.

The present invention will be described below based on examples, but the present invention is not limited thereto. Unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass."

(Average primary particle size of pigment)
The average primary particle size of the pigment was measured by a method in which a transmission electron microscope (TEM) was used to directly measure the size of the primary particles from an electron microscope photograph. Specifically, the minor axis diameter and major axis diameter of each pigment primary particle were measured, and the average was taken as the particle size of the pigment primary particle. Next, the volume (mass) of each particle was calculated for 100 or more pigment particles by approximating it to a cube of the calculated particle size, and the volume average particle size was taken as the average primary particle size.

<Method of manufacturing fine pigments>
(Red Microparticulate Pigment (A-1))
200 parts of C.I. Pigment Red 254 (BASF "S3610CF"), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho) and kneaded at 80°C for 6 hours. Next, this kneaded mixture was added to 8000 parts of warm water, heated to 80°C and stirred for 2 hours to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85°C for 24 hours to obtain 190 parts of finely divided pigment (A-1). The average primary particle size was 27.6 nm.

(Purple Micronized Pigment (A-2))
100 parts of purple pigment C.I. Pigment Violet 23 ("LIONOGEN VIOLET FG-6140" manufactured by Toyo Color Co., Ltd.), 800 parts of ground salt, and 100 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 70 ° C. for 12 hours. This mixture was added to 3000 parts of hot water, heated to about 70 ° C. and stirred with a high-speed mixer for about 1 hour to form a slurry, filtered and washed with water repeatedly to remove salt and solvent, and then dried at 80 ° C. for 24 hours to obtain 95 parts of purple fine pigment (A-2). The average primary particle diameter of the obtained pigment was 53.7 nm.

(Blue Micronized Pigment (A-3))
100 parts of blue pigment C.I. Pigment Blue 15:6 ("Lionol Blue ES" manufactured by Toyo Color Co., Ltd.), 800 parts of ground salt, and 100 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 70°C for 12 hours. This mixture was added to 3000 parts of hot water, heated to about 70°C and stirred with a high-speed mixer for about 1 hour to form a slurry, filtered and washed with water repeatedly to remove salt and solvent, and then dried at 80°C for 24 hours to obtain 98 parts of blue fine pigment (A-3). The average primary particle diameter of the obtained pigment was 28.3 nm.

<Production of dye derivative>
(Dye derivatives (B-1) to (B-3))
The dye derivative having the structure shown below was prepared with reference to the literature mentioned in the description of the dye derivative above.

(Mass average molecular weight of acidic resin-type dispersing resin (C))
The mass average molecular weight (Mw) of the resin is the polystyrene-equivalent mass average molecular weight (Mw) measured using a TSKgel column (manufactured by Tosoh Corporation) and a GPC (manufactured by Tosoh Corporation, HLC-8120GPC) equipped with an RI detector, using THF as a developing solvent.

(Acid value of acidic resin-type dispersing resin (C))
The resin acid value is the acid value (mgKOH/g) measured according to the potentiometric titration method of JIS K 0070 and converted into the non-volatile content.

<Method for producing acidic resin-type dispersing resin (C)>
(Acidic resin type dispersant C1-1)
In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 12 parts of 3-mercapto-1,2-propanediol, 16 parts of trimellitic anhydride, 0.01 parts of monobutyltin oxide, and 150 parts of PGMAc were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 100 ° C. and reacted for 7 hours. After confirming that 98% or more of the acid anhydride was half-esterified by measuring the acid value, the temperature in the system was cooled to 70 ° C., 60 parts of ETERNACOLL OXMA (manufactured by Ube Industries), 20 parts of methyl methacrylate, 30 parts of tert-butyl acrylate, and 90 parts of tert-butyl methacrylate were charged, and 0.5 parts of 2,2'-azobisisobutyronitrile and 100 parts of PGMAc were added and reacted for 10 hours. It was confirmed that the polymerization had progressed to 95% by measuring the solid content, and the reaction was terminated. PGMAc was added to adjust the nonvolatile content to 50%, obtaining a dispersant (C1-1) with an acid value of 59 and a weight average molecular weight of 13,000.

(Synthesis of Acidic Resin-Type Dispersants (C1-2 to 5, C2-1 to 2, CB-1 to 2))
Except for changing the raw materials shown in Table 1, acidic resin-type dispersants (C1-2 to 5, C2-1 to 2, CB-1 to 2) were synthesized in the same manner as for the acidic resin-type dispersant C1-1.

<Production of Colored Composition>
[Example 1]
(Preparation of Colored Composition (PP-1))
The mixture below was stirred and mixed to be homogeneous, and then dispersed for 5 hours in an Eiger mill ("Mini Model M-250 MKII" manufactured by Eiger Japan Co., Ltd.) using zirconia beads having a diameter of 0.5 mm. The mixture was then filtered through a 5.0 μm filter to prepare a colored composition (PP-1).
Red fine pigment (A-1): 12.0 parts Dye derivative (B-1): 2.0 parts Acidic resin type dispersant (C1-1): 12.0 parts Acidic resin type dispersant (C2-1): 4.0 parts Propylene glycol monomethyl ether acetate (PGMAc): 80.0 parts
However, Example 1 is a reference example.

[Examples 2 to 43, Comparative Examples 1 to 4]
Colored compositions (PP-2 to PP-47) were prepared in the same manner as in Example 1, except that the compositions were changed to those shown in Table 2.
However, Examples 2 to 32 are reference examples.

<Preparation of binder resin solution>
(Binder resin solution: J-1)
A separable 4-neck flask was fitted with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirrer. 70.0 parts of methoxypropyl acetate was charged into the reaction vessel, which was then heated to 80°C and substituted with nitrogen in the reaction vessel. A mixture of 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide modified acrylate ("Aronix M110" manufactured by Toagosei Co., Ltd.), and 0.4 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for another 3 hours to obtain a solution of an acrylic resin having a mass average molecular weight of 26,000. After cooling to room temperature, about 2 g of the resin solution was sampled and dried by heating at 180°C for 20 minutes to measure the non-volatile content. Methoxypropyl acetate was added to the previously synthesized resin solution so that the non-volatile content became 20%, to prepare a binder resin solution (J-1).

<Evaluation of Colored Composition>
The obtained colored composition was evaluated for heat resistance, film remaining rate, storage stability (viscosity), and filterability as described below.

(Evaluation of heat resistance)
The obtained colored composition was applied to a glass substrate of 100 mm x 100 mm and 1.1 mm thickness using a spin coater so that the chromaticity under C light source was y = 0.100, then dried at 60 ° C for 5 minutes, and then heated at 230 ° C for 20 minutes and allowed to cool to prepare a coating film substrate. The prepared coating film substrate was heat-treated at 230 ° C, and the chromaticity ([L * (1), a * (1), b * (1)]) under C light source of the obtained coating film was measured using a microspectrophotometer (Olympus Optical Co., Ltd. "OSP-SP100"). Thereafter, as a heat resistance test, the substrate was heated at 230 ° C for 1 hour, and the chromaticity ([L * (2), a * (2), b * (2)]) under C light source was measured, and the color difference ΔEab * was calculated according to the following formula and evaluated in the following three stages.
ΔEab*=√((L*(2)- L*(1))2 +(a*(2)-a*(1))2+(b*(2)-b*(1))2 )
◎: ΔEab* is less than 3.5 ◯: ΔEab* is 3.5 or more and less than 5.0 △: ΔEab* is 5.0 or more and less than 6.5 ×: ΔEab* is 6.5 or more

(Evaluation of film remaining rate)
The obtained colored composition was applied to a glass substrate of 100 mm x 100 mm and 1.1 mm thickness using a spin coater so that the chromaticity under C light source was y = 0.100, and then dried at 60 ° C for 5 minutes, and the thickness (1) of the obtained coating film was measured using a stylus surface profiler (Veeco's "Dektak 8"). The coating film was then heated at 230 ° C for 20 minutes and allowed to cool, and the thickness (2) of the obtained coating film was again measured using a stylus surface profiler (Veeco's "Dektak 8"). The rate of change in the film thickness was calculated using the following formula and evaluated in the following three stages.
Rate of change = film thickness (2) / film thickness (1) (%)
◯: 80% or more △: 75% or more but less than 80% ×: Less than 75%

(Evaluation of storage stability (viscosity evaluation))
The viscosity of the obtained colored composition was measured immediately after preparation and after storage at 10° C. for one month using an E-type viscometer. The ratio of (viscosity after storage for one month)/(viscosity immediately after preparation) was calculated and evaluated according to the following criteria. ⊚ indicates a very good level, ◯ indicates a good level, △ indicates a practical level, and × indicates a level not suitable for practical use.
◎: Viscosity ratio is 1.00 or more and less than 1.02. ○: Viscosity ratio is 1.02 or more and less than 1.05. △: Viscosity ratio is 1.05 or more and less than 1.10. ×: Viscosity ratio is 1.10 or more.

(Evaluation of filterability)
10 g of the obtained colored composition was passed through a filter (φ0.2 μm, manufactured by ADVANTEC, model number: 39115221) under nitrogen pressure (0.3 MPa), the amount of the colored composition that passed through the filter was measured, and the result was evaluated according to the following criteria: ◎ is a very good level, ◯ is a good level, △ is a practical level, and × is a level not suitable for practical use.
◎: Filtration amount is 8.0 g or more. ○: Filtration amount is 5.0 g or more and less than 8.0 g. △: Filtration amount is 3.0 g or more and less than 5.0 g. ×: Filtration amount is 3.0 g or less.

The results of the evaluation using the above methods are shown in Table 3.

As shown in Examples 1 to 43, the colorant (A), the dye derivative (B), the acidic resin-type dispersant (C1) in which the content of structural units derived from ethylenically unsaturated monomers having oxetane groups is 20% by mass or more and 100% by mass or less when the vinyl polymerization portion of the resin-type dispersant is taken as 100% by mass, and the acidic resin-type dispersant (C2) that does not contain structural units derived from ethylenically unsaturated monomers having oxetane groups showed excellent properties in all evaluation items.

Furthermore, the acidic resin-type dispersant (C1) and/or (C2) has a polyester portion having a carboxyl group formed by reacting an acid anhydride group in one or more acid anhydrides selected from tetracarboxylic acid anhydrides and tricarboxylic acid anhydrides with a hydroxyl group in a hydroxyl group-containing compound, and a vinyl polymer portion formed by radical polymerization of an ethylenically unsaturated monomer, thereby improving the dispersion state and enabling the production of a dispersion with extremely excellent storage stability.

Furthermore, by including copper phthalocyanine pigment in colorant (A), a dispersion with excellent heat resistance was obtained.

Furthermore, the content of acidic resin-type dispersant (C1) is 30% by mass or more and less than 70% by mass, out of a total of 100% by mass of acidic resin-type dispersant (C1) and acidic resin-type dispersant (C2), so that the heat resistance, film remaining rate, storage stability, and filterability are specifically improved, and an extremely excellent dispersion can be obtained.

In the comparative examples, results that satisfied all items were not obtained, proving the effectiveness of the present invention.

<Production of Photosensitive Coloring Composition>
[Example 44]
(Photosensitive coloring composition (PR-1))
The following mixture was stirred and mixed to a uniform consistency, and then filtered through a 1.0 μm filter to prepare a photosensitive coloring composition (PR-1).
Colored composition (PP-1): 60.0 parts Binder resin solution (J-1): 11.0 parts Polymerizable monomer 1: 3.6 parts Dipentaerythritol penta- and hexaacrylate ("Aronix M402" manufactured by Toagosei Co., Ltd.)
Polymerizable monomer 2: 1.0 part trimethylolpropane PO modified triacrylate ("Aronix M310" manufactured by Toagosei Co., Ltd.)
Photopolymerization initiator 1: 0.6 parts ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(0-acetyloxime)
("Irgacure OXE02" manufactured by BASF Japan)
Photopolymerization initiator 2: 0.6 parts 1-(N-4-benzoylphenyl-carbazol-3-yl)-butane-1,2-dione-2-oxime-O-acetate Cyclohexanone: 5.2 parts Propylene glycol monomethyl ether acetate: 18.0 parts
However, Example 44 is a reference example.

[Examples 45 to 86, Comparative Examples 5 to 8]
(Photosensitive coloring composition (PR-2 to PR-47))
Photosensitive coloring compositions (PR-2 to PR-47) were prepared in the same manner as in Example 44, except that the coloring composition was changed to the coloring composition shown in Table 4.
However, Examples 45 to 75 are for reference only.

<Evaluation of Photosensitive Coloring Composition>
The obtained colored composition was evaluated for heat resistance, film remaining rate, pattern adhesion, storage stability (viscosity), and filterability as described below.

(Filter Segment Formation)
The obtained photosensitive coloring composition was applied to a glass substrate of 10 cm length x 10 cm width by spin coating, and then heated in a clean oven at 70 ° C for 15 minutes to remove the solvent, and a coating of about 2 μm was obtained. Next, the glass substrate was cooled to room temperature, and then exposed to ultraviolet light through a photomask of 100 μm width (pitch 200 μm) and 25 μm width (pitch 50 μm) stripe patterns using an ultra-high pressure mercury lamp. Then, the substrate was spray-developed using an aqueous sodium carbonate solution at 23 ° C, washed with ion-exchanged water, air-dried, and heated in a clean oven at 230 ° C for 30 minutes to prepare a filter segment. The spray development was performed for each coating of the photosensitive coloring composition in the shortest time possible to form a pattern without any residual development, and this was defined as the appropriate development time. The thickness of the coating film was measured using Dektak 3030 (manufactured by Japan Vacuum Technology Co., Ltd.).

(Evaluation of heat resistance)
The obtained photosensitive coloring composition was applied to a glass substrate of 100 mm x 100 mm and 1.1 mm thickness using a spin coater so that the chromaticity under C light source was y = 0.100, then dried at 60 ° C for 5 minutes, and then heated at 230 ° C for 20 minutes and allowed to cool to prepare a coating substrate. The chromaticity ([L * (1), a * (1), b * (1)]) under C light source of the prepared coating substrate was measured using a microspectrophotometer (Olympus Optical Co., Ltd. "OSP-SP100"). Thereafter, as a heat resistance test, the substrate was heated at 230 ° C for 1 hour, and the chromaticity ([L * (2), a * (2), b * (2)]) under C light source was measured, and the color difference ΔEab * was calculated according to the following formula and evaluated in the following three stages.
ΔEab*=√((L*(2)- L*(1))2 +(a*(2)-a*(1))2+(b*(2)-b*(1))2 )
◎: ΔEab* is less than 3.5 ◯: ΔEab* is 3.5 or more and less than 5.0 △: ΔEab* is 5.0 or more and less than 6.5 ×: ΔEab* is 6.5 or more

(Evaluation of film remaining rate)
The obtained photosensitive coloring composition was applied to a glass substrate of 100 mm x 100 mm and 1.1 mm thickness using a spin coater so that the chromaticity was y = 0.100 with a C light source, and then dried at 60 ° C for 5 minutes, and the thickness (1) of the obtained coating film was measured using a stylus surface profiler (Veeco's "Dektak 8"). The coating film was then heated at 230 ° C for 20 minutes, allowed to cool, and the thickness (2) of the obtained coating film was measured again using a stylus surface profiler (Veeco's "Dektak 8"). The rate of change in the film thickness was calculated using the following formula and evaluated in the following three stages.
Rate of change = film thickness (2) / film thickness (1) (%)
◯: 80% or more △: 75% or more but less than 80% ×: Less than 75%

(Evaluation of Pattern Adhesion)
The obtained filter segments were examined in transmission mode using an optical microscope (ECLIPSE LV100POL Model, manufactured by Nikon Corporation) to check for the disappearance of the 1 μm to 50 μm pattern. The pattern adhesion was evaluated according to the following criteria, based on how fine the pattern remained on the glass substrate.
⊚: All patterns of 4 μm or more remain. Excellent.
◯: All patterns of 8 μm or more remain. Good.
Δ: All patterns of 15 μm or more remain. Practical use is possible.
×: Patterns of 15 μm or more are lost in some places. Not practical.

(Evaluation of storage stability (viscosity evaluation))
The viscosity of the obtained photosensitive coloring composition was measured immediately after preparation and after storage at 10° C. for one month using an E-type viscometer. The ratio of (viscosity after storage for one month)/(viscosity immediately after preparation) was calculated and evaluated according to the following criteria. In addition, ◎ is a very good level, ◯ is a good level, △ is a practical level, and × is a level not suitable for practical use.
◎: Viscosity ratio is 1.00 or more and less than 1.02. ○: Viscosity ratio is 1.02 or more and less than 1.05. △: Viscosity ratio is 1.05 or more and less than 1.10. ×: Viscosity ratio is 1.10 or more.

(Evaluation of filterability)
10 g of the obtained photosensitive coloring composition was passed through a filter (φ0.2 μm, manufactured by ADVANTEC, model number: 39115221) under nitrogen pressure (0.3 MPa), the amount of the composition that passed through the filter was measured, and the composition was evaluated according to the following criteria. Here, ◎ is a very good level, ◯ is a good level, △ is a practical level, and × is a level that is not suitable for practical use.
◎: Filtration amount is 8.0 g or more. ○: Filtration amount is 5.0 g or more and less than 8.0 g. △: Filtration amount is 3.0 g or more and less than 5.0 g. ×: Filtration amount is 3.0 g or less.

The results of the evaluation using the above methods are shown in Table 5.

The photosensitive coloring compositions also showed similar results to those of the coloring compositions shown in Examples 45 to 86 and Comparative Examples 5 to 8.

Claims (5)

A coloring composition comprising a colorant (A), a dye derivative (B), and an acidic resin-type dispersant (C) having a vinyl polymer portion,
Colorant (A) comprises C.I. Pigment Blue 15:6;
The dye derivative (B) contains a phthalocyanine dye derivative ,
The acidic resin-type dispersant (C) contains the following acidic resin-type dispersant (C1) and acidic resin-type dispersant (C2),
A coloring composition characterized in that the content of the acidic resin type dispersant (C1) is 30 mass% or more and less than 70 mass% in a total of 100 mass% of the acidic resin type dispersant (C1) and the acidic resin type dispersant (C2).
Acidic resin type dispersant (C1): An acidic resin type dispersant in which the content of structural units derived from an ethylenically unsaturated monomer having an oxetane group is 20% by mass or more and 100% by mass or less, when the vinyl polymerization portion of the resin type dispersant is taken as 100% by mass.
Acidic resin type dispersant (C2): An acidic resin type dispersant that does not contain a structural unit derived from an ethylenically unsaturated monomer having an oxetane group. The coloring composition according to claim 1, characterized in that the acidic resin-type dispersant (C1) and/or (C2) has a polyester portion having a carboxyl group, which is formed by reacting an acid anhydride group in one or more acid anhydrides selected from tetracarboxylic acid anhydrides and tricarboxylic acid anhydrides with a hydroxyl group in a hydroxyl group-containing compound, and a vinyl polymer portion formed by radical polymerization of an ethylenically unsaturated monomer. The coloring composition according to claim 1 or 2, further comprising a polymerizable compound (D) and/or a photopolymerization initiator (E). A color filter having filter segments formed using the coloring composition according to any one of claims 1 to 3. A liquid crystal display device comprising the color filter according to claim 4.